Secondary Zinc-Manganese Dioxide Batteries for High Power Applications

ABSTRACT

In an embodiment, a secondary Zn—MnO 2  battery comprises a battery housing, a MnO 2  cathode, a Zn anode, and an electrolyte solution. The MnO 2  cathode, the Zn anode, and the electrolyte solution are disposed within the battery housing, and the MnO 2  cathode comprises a MnO 2  cathode mixture and a current collector. The MnO 2  cathode mixture is in electrical contact with at least a portion of an outer surface of the current collector, and the MnO 2  cathode has a porosity of from about 5 vol. % to about 90 vol. %, based on the total volume of the MnO 2  cathode mixture of the MnO 2  cathode.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a filing under 35 U.S.C. 371 of InternationalApplication No. PCT/US2013/069166 filed Nov. 8, 2013, entitled“Secondary zinc-manganese dioxide batteries for high powerapplications,” which claims the benefit of U.S. Provisional ApplicationNos. 61/724,873 filed on Nov. 9, 2012 and 61/732,926 filed on Dec. 3,2012, each of which are incorporated herein by reference in theirentirety for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The invention described and claimed herein was made in part utilizingfunds supplied by the U.S. Department of Energy under Contract No.DE-AR0000150. The Government has certain rights in this invention.

REFERENCE TO A MICROFICHE APPENDIX

Not applicable.

BACKGROUND

This disclosure relates to methods of assembling and/or manufacturingsecondary alkaline batteries. More specifically, it relates tocompositions and methods for assembling and/or manufacturing secondaryzinc-manganese dioxide batteries for high power applications.

As the world population increases and the available resources arefinite, energy production and storage is of paramount importance to themodern contemporary society. An important class of energy storagesystems is represented by rechargeable batteries, also known assecondary batteries, secondary electrochemical cells or secondary cells.Secondary batteries represent an excellent class of electrical energystorage technologies for matching energy consumption with production,especially for the integration of renewable sources; however thedevelopment of secondary batteries is limited in part by the availablematerials (e.g., electrodes, electrolyte, etc.) and strategies forassembling such batteries.

Secondary batteries most commonly include lead-acid batteries,nickel-cadmium (NiCd) batteries, nickel-metal hydride (NiMH) batteries,lithium-ion (Li-ion) batteries, and lithium-ion polymer (Li-ion polymer)batteries. Recently, secondary alkaline batteries have also beendeveloped. Most commercial alkaline batteries are primary use (e.g.,primary batteries, primary electrochemical cells or primary cells),meaning that after a single discharge primary batteries are disposed ofand replaced. Primary alkaline batteries are produced in high volume atlow cost by numerous commercial manufacturers.

Secondary alkaline batteries have recently come to market based ontechnology developed by Battery Technologies Inc. in Canada (U.S. Pat.No. 4,957,827), which was licensed to Pure Energy, Grandcell,EnviroCell, and Rayovac. These secondary alkaline batteries requireproprietary chargers meant to improve cycleability (U.S. Pat. No.7,718,305). Furthermore, the lifetime of the secondary alkalinebatteries is limited due to the high depth of discharge these batteriesexperience in commercial applications. Due to these limitations,secondary alkaline batteries have not achieved widespread adoption todate.

The state of the art cathode design for both primary and secondaryalkaline batteries typically includes an active (i.e., electroactive)material (e.g., nickel oxide, silver oxide, manganese dioxide (MnO₂),etc.) and a conductor (i.e., conductive, conducting) material (typicallygraphite) with some additives. The cathode materials are all compactedand pressed into a cavity, which is either tubular or planar, along withan anode and an electrolyte solution that has been absorbed into aseparator material.

Zn—MnO₂ batteries are well known as primary alkaline batteries, but theirreversibility associated with the manganese dioxide (MnO₂) electrodeand dendrite formation at the zinc (Zn) electrode upon cycling, havelimited the application of Zn—MnO₂ batteries as a secondary batteries.Efforts to develop secondary Zn—MnO₂ batteries date back more than 40years, with many unsuccessful attempts made to commercialize it. Some ofthe problems associated with Zn electrodes include shape change anddendritic shorting, and some of the problems associated with MnO₂electrodes are manganese oxides-related insolubility and reactionirreversibility, and all these problems limit the cycle life ofsecondary Zn—MnO₂ batteries.

A major shortcoming of Zn electrodes is a limited cycle life caused bymaterial migration/shape change and dendritic shorting. In particular,the Zn electrode in nickel-zinc battery systems has a tendency to becomemisshapen due to anisotropic growth of the Zn deposited on the electrodeduring repeated charging. To reduce shape change, many approaches havebeen tried with varying degrees of success, including modifications toelectrolyte, zinc electrode design, or cell design. These approachesgenerally involve reducing either the solubility or the concentrationgradients of the zinc in the electrolyte. For example, U.S. Pat. No.4,358,517 and U.S. Pat. No. 5,863,676 disclose methods involving the useof calcium oxide or hydroxide additives to the zinc electrode.

To reduce the likelihood of dendritic shorting, micro-porous barrierfilms, positioned between the electrodes, have been tried. Mostrecently, micro-porous polyolefin separators (e.g., CELGARD batteryseparators) have had some success, but these materials are quiteexpensive. A sealed starved mode of cell operation is also thought to bebeneficial with respect to elimination of dendrites. Oxygen generated onan overcharge of a positive nickel oxide electrode is thought to oxidizemetallic zinc dendrites. Since all zinc electrodes evolve small amountsof hydrogen gas on standing, some means of oxidizing hydrogen may alsobe used in a sealed cell, or else the cell pressure may increase withoutlimit.

Another approach to improving cycle life involves modifications to thebattery electrolyte. In this regard, many different additives to theelectrolyte have been tried. The modifications to the electrolytetypically have as their object to reduce the solubility of zinc, andthereby reduce shape change. Typical examples of this approach includefluoride/carbonate mixtures, as disclosed in U.S. Pat. No. 5,453,336 andborates, phosphates, and arsenates mixtures, as disclosed in U.S. Pat.No. 5,215,836.

Some alkaline batteries having a Zn-based anode mitigate dendriteformation by allowing an electrolyte solution to flow rather than remainstatic in a separator. Increased cycle life has been demonstrated withNiOOH/Zn batteries (PCT Application No. U.S. 2010/052582, WO2011/047105). In such a secondary alkaline battery, the anode (e.g., aNi-coated plate substrate for Zn deposition), and the cathode (e.g., asintered NiOOH sheet) are structurally stable (even without support) andare thus easily inserted into a battery system with a flowingelectrolyte solution. However, this battery system has not yet beenapplied to Zn—MnO₂ batteries due to the undesirable irreversibilityassociated with the MnO₂ cathode.

The development of a material phase of Mn₃O₄ (product of second electronreaction at a battery cathode) that cannot be recharged (re-oxidized) togamma phase MnO₂ also reduces the cycle life of the battery and hasprevented past cells comprising MnO₂ from achieving more than 50 cycles.Many approaches have been tried to improve the cycle life ofelectrolytic manganese dioxide. For example, U.S. Pat. No. 3,024,297describes the formation of a cathode depolarizer mix. German Patent No.3,337,568 describes titanium doping of electrolytic manganese dioxidefor improved cycle life.

As such, there exists a need for improved secondary alkaline batteriesemploying Zn-based anodes and MnO₂-based cathodes and methods of makingsame.

SUMMARY

In an embodiment, a secondary Zn—MnO₂ battery comprises a batteryhousing, a MnO₂ cathode, a Zn anode, and an electrolyte solution. TheMnO₂ cathode, the Zn anode, and the electrolyte solution are disposedwithin the battery housing, and the MnO₂ cathode comprises a MnO2cathode mixture and a current collector. The MnO₂ cathode mixture is inelectrical contact with at least a portion of an outer surface of thecurrent collector, and the MnO₂ cathode has a porosity of from about 5vol. % to about 90 vol. %, based on the total volume of the MnO₂ cathodemixture of the MnO₂ cathode. The Zn anode and the MnO₂ cathodecapacities may be balanced. At least one of the Zn anode or the MnO₂cathode may comprise a pasted configuration. At least one of the MnO₂cathode or the Zn anode may have a thickness of from about 100 micronsto about 1,000 microns. At least one of the MnO₂ cathode or the Zn anodemay have a thickness of about 400 microns. At least one of the MnO₂cathode or the Zn anode may be further wrapped in an electrode separatormembrane. The electrode separator membrane may comprise a polymericmembrane, a sintered polymer film membrane, a polyolefin membrane, apolyolefin nonwoven membrane, a cellulose membrane, a cellophane, abattery-grade cellophane, a sintered polyolefin film membrane, ahydrophilically modified polyolefin membrane, or any combinationsthereof. The MnO₂ cathode mixture may comprise MnO₂ in an amount of fromabout 45 wt. % to about 80 wt. %, an electronically conductive materialin an amount of from about 10 wt. % to about 45 wt. %, and a binder inan amount of from about 2 wt. % to about 10 wt. %, based on a totalweight of the MnO₂ cathode mixture. The MnO₂ may comprise electrolyticmanganese dioxide, the electronically conductive material may comprisecarbon, graphite, graphite powder, graphite powder flakes, graphitepowder spheroids, carbon black, activated carbon, conductive carbon,amorphous carbon, glassy carbon, or any combination thereof; and thebinder may comprise a polymer; a fluoropolymer, polytetrafluoroethylene(PTFE), a copolymer of tetrafluoroethylene and propylene; polyvinylidenefluoride (PVDF), a copolymer of styrene and butadiene, styrene-butadienerubber (SBR); a conducting polymer, polyaniline, polypyrrole,poly(3,4-ethylenedioxylthiophene) (PEDOT), copolymers of3,4-ethylenedioxylthiophene with various co-monomers (e.g., PEDOT withvarious dopants), a copolymer of 3,4-ethylenedioxylthiophene andstyrenesulfonate (PEDOT:PSS), polyvinyl alcohol (PVA), hydroxymethylcellulose (HMC), carboxymethyl cellulose (CMC), or any combinationthereof. The MnO₂ cathode mixture may also include a metal, Bi, Sr, Ca,Ba, an oxide thereof, a hydroxides thereof, a nitrate thereof, achlorides thereof, or any combination thereof. The MnO₂ cathode maycomprise a pasted MnO₂ cathode. The MnO₂ cathode may comprise a firstMnO₂ cathode dried sheet, a second MnO₂ cathode dried sheet, and thecurrent collector. The first MnO₂ cathode dried sheet may be pressedonto a first side of the current collector, the second MnO₂ cathodedried sheet may be pressed onto a second side of the current collector,and the first and the second MnO₂ cathode dried sheets may be pressedonto their respective sides of the current collector at a pressure offrom about 3,000 psi to about 10,000 psi. The MnO₂ cathode mixture maybe in electrical contact with both the first side and the second side ofthe current collector. The current collector may comprise a porous metalcollector, a metal conductive mesh, a metal conductive interwoven mesh,a metal conductive expanded mesh, a metal conductive screen, a metalconductive plate, a metal conductive foil, a metal conductive perforatedplate, a metal conductive perforated foil, a metal conductive perforatedsheet, a sintered porous metal conductive sheet, a sintered metalconductive foam, an expanded conductive metal, a perforated conductivemetal, or any combination thereof. The current collector may comprise ametal collector pocketed assembly. The current collector may comprise acurrent collector substrate comprising graphite, carbon, a metal, analloy, steel, copper, nickel, silver, platinum, brass, or anycombination thereof. The current collector may comprise a metal, nickel,silver, cadmium, tin, lead, bismuth, or any combinations thereofdeposited on the current collector substrate. The current collector maycomprise a current collector tab, and the current collector tab may bein electrical contact with an outer surface of the MnO₂ cathode.

In some embodiments, the secondary Zn—MnO₂ battery may comprise anon-flow secondary Zn—MnO₂ battery, the battery housing may comprise anon-flow battery housing, wherein the Zn anode comprises a non-flow cellZn anode, and the electrolyte solution may comprise a non-flow cellelectrolyte solution. The non-flow secondary Zn—MnO₂ battery maycomprise a prismatic configuration. The non-flow cell Zn anode maycomprise a non-flow cell Zn anode mixture and a current collector, andthe non-flow cell Zn anode mixture may be in electrical contact with atleast a portion of an outer surface of the current collector. Thenon-flow cell Zn anode may have a porosity of from about 5 vol. % toabout 90 vol. % based on the total volume of the non-flow cell Zn anodemixture of the non-flow cell Zn anode. The non-flow cell Zn anodemixture may comprise Zn in an amount of from about 50 wt. % to about 90wt. %, ZnO in an amount of from about 5 wt. % to about 20 wt. %, anelectronically conductive material in an amount of from about 5 wt. % toabout 20 wt. %, and a binder in an amount of from about 2 wt. % to about10 wt. %, based on the total weight of the non-flow cell Zn anodemixture. The non-flow cell Zn anode may comprise a pasted non-flow cellZn anode. The non-flow cell electrolyte solution may comprise ahydroxide, a potassium hydroxide, a sodium hydroxide, a lithiumhydroxide, or any combination thereof in a concentration of from about 1wt. % to about 50 wt. % based on the total weight of the non-flow cellelectrolyte solution. The non-flow secondary Zn—MnO₂ battery may becharacterized by a cycle life of equal to or greater than about 5,000cycles.

In some embodiments, the secondary Zn—MnO₂ battery comprises aflow-assisted secondary Zn—MnO₂ battery, wherein the battery housingcomprises a flow-assisted battery housing, wherein the Zn anodecomprises a flow-assisted cell Zn anode, and wherein the electrolytesolution comprises a flow-assisted cell electrolyte solution. Theflow-assisted secondary Zn—MnO₂ battery may comprise a MnO₂ cathodeplate, and the plate may have flat surfaces. The flow-assisted cell Znanode may comprise electrodeposited Zn and a current collector, and theelectrodeposited Zn may be disposed on and in electrical contact withthe current collector. The flow-assisted cell electrolyte solution maycomprise a hydroxide, potassium hydroxide, sodium hydroxide, lithiumhydroxide, or combinations thereof in a concentration of from about 1wt. % to about 50 wt. % based on the total weight of the non-flow cellelectrolyte solution. The flow-assisted cell electrolyte solution maycomprise ZnO in an amount of from about 0 g/L to about 200 g/L. Theflow-assisted secondary Zn—MnO2 battery may be configured tocontinuously circulate the flow-assisted cell electrolyte solutionthrough the flow-assisted battery housing.

In an embodiment, a method for producing energy comprises discharging anon-flow secondary Zn—MnO₂ battery to a discharge voltage to produceenergy, charging the non-flow secondary Zn—MnO₂ battery to a chargevoltage, and repeating the discharging and the charging of theflow-assisted secondary Zn—MnO₂ battery at least once. The non-flowsecondary Zn—MnO₂ battery comprises: a non-flow battery housing, a MnO₂cathode, a non-flow cell Zn anode, and a non-flow cell electrolytesolution. The MnO₂ cathode, the non-flow cell Zn anode, and the non-flowcell electrolyte solution are supported within the non-flow batteryhousing, and at least a portion of the Zn of the non-flow cell Zn anodeis oxidized during the discharging. At least a portion of the ZnO fromthe non-flow cell Zn anode mixture is reduced to Zn during the charging,and the non-flow secondary Zn—MnO₂ battery is characterized by a cyclelife of equal to or greater than about 5,000 cycles. The MnO₂ cathodemay comprise a MnO₂ cathode mixture and a current collector. The MnO₂cathode mixture may be in electrical contact with at least a portion ofan outer surface of the current collector, and the MnO₂ cathode may havea porosity of from about 5 vol. % to about 90 vol. % based on the totalvolume of the MnO₂ cathode mixture of the MnO₂ cathode. The non-flowcell Zn anode may comprise a non-flow cell Zn anode mixture and acurrent collector. The non-flow cell Zn anode mixture may be inelectrical contact with at least a portion of an outer surface of thecurrent collector, and the non-flow cell Zn anode may have a porosity offrom about 5 vol. % to about 90 vol. % based on the total volume of thenon-flow cell Zn anode mixture of the non-flow cell Zn anode. Thenon-flow cell Zn anode mixture may comprise Zn in an amount of fromabout 50 wt. % to about 90 wt. %, ZnO in an amount of from about 5 wt. %to about 20 wt. %, an electronically conductive material in an amount offrom about 5 wt. % to about 20 wt. %, and a binder in an amount of fromabout 2 wt. % to about 10 wt. %, based on the total weight of thenon-flow cell Zn anode mixture. The non-flow cell electrolyte solutionmay comprise a hydroxide, a potassium hydroxide, a sodium hydroxide, alithium hydroxide, or any combination thereof in a concentration of fromabout 1 wt. % to about 50 wt. % based on the total weight of thenon-flow cell electrolyte solution. The non-flow secondary Zn—MnO₂battery may be charged when assembled.

In an embodiment, a method for producing energy comprises charging theflow-assisted secondary Zn—MnO₂ battery to a charge voltage, dischargingthe flow-assisted secondary Zn—MnO₂ battery to a discharge voltage toproduce energy, and continuously circulating the flow-assisted cellelectrolyte solution through the flow-assisted battery housing duringthe charging and the discharging. The flow-assisted secondary Zn—MnO₂battery comprises: a flow-assisted battery housing, a MnO₂ cathode, aflow-assisted cell Zn anode comprising a current collector, and aflow-assisted cell electrolyte solution. The MnO₂ cathode, theflow-assisted cell Zn anode, and the flow-assisted cell electrolytesolution are supported within the flow-assisted battery housing, and ZnOfrom the flow-assisted cell electrolyte solution is deposited aselectrodeposited Zn on the current collector of the flow-assisted cellZn anode during the charging. At least a portion of the electrodepositedZn of the flow-assisted cell Zn anode is oxidized and transferred backinto the flow-assisted cell electrolyte solution during the discharging.The method may also include discharging the flow-assisted secondaryZn—MnO₂ battery to a final voltage below the discharge voltage. Theelectrodeposited Zn of the flow-assisted cell Zn anode may be completelyremoved from the current collector. Continuously circulating theflow-assisted cell electrolyte solution through the flow-assistedbattery housing may occur during the discharging of the flow-assistedsecondary Zn—MnO₂ battery to a final voltage below the dischargevoltage. The MnO₂ cathode may comprise a MnO₂ cathode mixture and asecond current collector, and the MnO₂ cathode mixture may be inelectrical contact with at least a portion of an outer surface of thesecond current collector. The MnO₂ cathode may have a porosity of fromabout 5 vol. % to about 90 vol. % based on the total volume of the MnO₂cathode mixture of the MnO₂ cathode. The flow-assisted cell electrolytesolution may comprise a hydroxide, a potassium hydroxide, a sodiumhydroxide, a lithium hydroxide, or any combination thereof in aconcentration of from about 1 wt. % to about 50 wt. % based on the totalweight of the non-flow cell electrolyte solution. The flow-assisted cellelectrolyte solution may comprise ZnO in an amount of from about 0 g/Lto about 200 g/L.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other structures for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent constructions do notdepart from the spirit and scope of the invention as set forth in theappended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present disclosure and theadvantages thereof, reference is now made to the following briefdescription, taken in connection with the accompanying drawings anddetailed description, wherein like reference numerals represent likeparts.

FIG. 1 displays the net stoichiometry of a Zn—MnO₂ battery.

FIG. 2 displays a cross-section schematic of an embodiment of afreestanding, self-supported MnO₂ cathode.

FIG. 3A displays a top view schematic of an embodiment of aflow-assisted secondary Zn—MnO₂ battery.

FIG. 3B displays a side view schematic of an embodiment of theflow-assisted secondary Zn—MnO₂ battery of FIG. 3A.

FIG. 4A displays a graph showing the viscosity behavior of an embodimentof a MnO₂ cathode mixture.

FIG. 4B displays an analysis of elastic versus viscous behavior of thedata from FIG. 4A.

FIG. 5 displays a graph showing the effect of MnO₂ cathode thickness ondischarge capacity in embodiments of non-flow secondary Zn—MnO₂batteries.

FIG. 6 displays a graph showing the effect of the electrode separatormembrane of the MnO₂ cathode on non-flow secondary Zn—MnO₂ batteries inan exemplary embodiment.

FIG. 7 displays a schematic representation of an embodiment of a currentcollector tab location on an electrode.

FIG. 8A displays a graph showing the effect of an embodiment of thecurrent collector tab location on non-flow secondary Zn—MnO₂ batteries.

FIG. 8B displays a graph showing the effect of electrode size andcurrent collector tab location on non-flow secondary Zn—MnO₂ batteriesin an exemplary embodiment.

FIG. 9 displays a graph showing the effect of the concentration ofhydroxide in the non-flow cell electrolyte solution on non-flowsecondary Zn—MnO₂ batteries in an exemplary embodiment.

FIG. 10 displays a graph showing the effect of the type of binder usedin MnO₂ cathode on the performance of non-flow secondary Zn—MnO₂batteries in an exemplary embodiment.

FIG. 11 displays a graph showing the cycle life of a non-flow secondaryZn—MnO₂ battery in an exemplary embodiment.

FIG. 12 displays a graph showing the discharge at different C-rates at0° C. for a non-flow secondary Zn—MnO₂ battery in an exemplaryembodiment.

FIG. 13 displays a scanning electron microscope image of cross-sectionof an embodiment of a freestanding, self-supported MnO₂ cathode.

FIG. 14 displays a graph showing capacity as a function of cycle numberfor a flow-assisted secondary Zn—MnO₂ battery in an exemplaryembodiment.

FIG. 15 displays a graph showing coulombic and energy efficiency as afunction of cycle number for a flow-assisted secondary Zn—MnO₂ batteryin an exemplary embodiment.

DETAILED DESCRIPTION

It should be understood at the outset that although an illustrativeimplementation of one or more embodiments are provided below, thedisclosed systems and/or methods may be implemented using any number oftechniques, whether currently known or in existence. The disclosureshould in no way be limited to the illustrative implementations,drawings, and techniques below, including the exemplary designs andimplementations illustrated and described herein, but may be modifiedwithin the scope of the appended claims along with their full scope ofequivalents.

Disclosed herein are embodiments of secondary Zn—MnO₂ batteries andmethods of making and using same. In an embodiment, the secondaryZn—MnO₂ batteries may comprise a Zn anode, a MnO₂ cathode and anelectrolyte. In some embodiments, the secondary Zn—MnO₂ batteries of thetype disclosed herein may employ a non-flow configuration, and suchbatteries may be referred to as “non-flow secondary Zn—MnO₂ batteries”for purposes of the present disclosure. In other embodiments, thesecondary Zn—MnO₂ batteries of the type disclosed herein may employ aflow-assisted configuration, and such batteries may be referred to as“flow-assisted secondary Zn—MnO₂ batteries” for purposes of the presentdisclosure.

Without wishing to be limited by theory, the two electrodes (i.e., a Znanode and a MnO₂ cathode) that are part of the secondary Zn—MnO₂ batteryhave different electrochemical potentials which are dictated by thechemistry that occurs at each electrode, and when such electrodes areconnected to an external device, electrons flow from the more negativeto the more positive potential electrode and electrical energy can beextracted by the external device/circuit. The charge balance in asecondary Zn—MnO₂ battery can be maintained by the transport of ionsthrough an ion transporter, such as for example an electrolyte. The netstoichiometry of a Zn—MnO₂ battery is depicted in FIG. 1, wherein thestandard cell potential associated with a Zn—MnO₂ battery is about 1.43V.

Disclosed herein are materials, methods, and systems for developingsecondary Zn—MnO₂ batteries comprising electrodes and an electrolyte,wherein the battery can be either in a non-flow configuration or in aflow-assisted configuration. Each of the components of the secondaryZn—MnO₂ batteries as well as methods of making and using same (e.g.,electrodes, active electrode materials, electrolyte compositions,electrochemical operation techniques, etc.) will be described in moredetail herein.

In an embodiment, a secondary Zn—MnO₂ battery may comprise a batteryhousing, a MnO₂ cathode, a Zn anode, and an electrolyte solution;wherein the MnO₂ cathode, the Zn anode, and the electrolyte solution aresupported within the battery housing. As will be appreciated by one ofskill in the art, and with the help of this disclosure, during theoperating life of the battery, while the battery is in a discharge phase(e.g., the battery is producing energy, thereby acting as a galvaniccell), the MnO₂ cathode is a positive electrode and the Zn anode is anegative electrode; and while the battery is in a recharging phase(e.g., the battery is consuming energy, thereby acting as anelectrolytic cell), the polarity of the electrodes is reversed, i.e.,the MnO₂ cathode becomes the negative electrode and the Zn anode becomesthe positive electrode.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, the number of electrodes in a secondary Zn—MnO₂ batteryis dependent upon the desired parameters for such secondary Zn—MnO₂battery. In an embodiment, the number and size of each of the electrodes(e.g., Zn anode, MnO₂ cathode) in a secondary Zn—MnO₂ battery can bechosen based on the properties of the electrodes, such that Zn anode andMnO₂ cathode capacities are balanced.

Non-Flow Secondary Zn—MnO₂ Battery

In an embodiment, the secondary Zn—MnO₂ battery comprises a non-flowsecondary Zn—MnO₂ battery, wherein the battery housing comprises anon-flow battery housing, the Zn anode comprises a non-flow cell Znanode, and the electrolyte solution comprises a non-flow cellelectrolyte solution.

In an embodiment, the non-flow secondary Zn—MnO₂ battery comprises thenon-flow battery housing, the non-flow cell Zn anode, the MnO₂ cathode,and the non-flow cell electrolyte solution, wherein the non-flow cell Znanode, the MnO₂ cathode, and the non-flow cell electrolyte solution maybe supported/located inside the non-flow battery housing. In anembodiment, the non-flow battery housing comprises a molded box orcontainer, such as for example a thermoplastic polymer molded box (e.g.,a polysulfone molded box), a thermoplastic olefin polymer molded box,etc.

In an embodiment, the electrodes (e.g., non-flow cell Zn anode, MnO₂cathode) of a non-flow secondary Zn—MnO₂ battery may be in any prismaticgeometry/configuration. In an embodiment, the non-flow secondary Zn—MnO₂battery excludes a non-prismatic geometry/configuration. While prismaticconfigurations are described herein, one of ordinary skill in the artwill appreciate that other, non-prismatic designs can be used. Forexample, a cylindrical or other design can also be used with theappropriate configuration of the electrodes as described herein.

In an embodiment, the non-flow cell Zn anode comprises a non-flow cellZn anode mixture and a current collector. While the present disclosurewill be discussed in detail in the context of non-flow cell zinc anodes,it should be understood that other materials, such as for example othermetals, aluminum, nickel, magnesium, etc., may be used as non-flow cellanodes or anode materials. Without wishing to be limited by theory, Znas part of the non-flow cell Zn anode mixture is an electrochemicallyactive material, and may participate in a redox reaction (according tothe reactions depicted in FIG. 1), thereby contributing to the overallvoltage of the battery, while the current collector has the purpose ofconducting current by enabling electron flow and does not significantlycontribute, or in some embodiments does not contribute at all, to theoverall voltage of the battery.

In an embodiment, the non-flow cell Zn anode mixture comprises Zn, zincoxide (ZnO), an electronically conductive material, and a binder. In anembodiment, Zn may be present in the non-flow cell Zn anode mixture inan amount of from about 50 wt. % to about 90 wt. %, alternatively fromabout 60 wt. % to about 80 wt. %, or alternatively from about 65 wt. %to about 75 wt. %, based on the total weight of the non-flow cell Znanode mixture. In an embodiment, Zn may be present in the non-flow cellZn anode mixture in an amount of about 85 wt. %, based on the totalweight of the non-flow cell Zn anode mixture.

In an embodiment, ZnO may be present in the non-flow cell Zn anodemixture in an amount of from about 5 wt. % to about 20 wt. %,alternatively from about 5 wt. % to about 15 wt. %, or alternativelyfrom about 5 wt. % to about 10 wt. %, based on the total weight of thenon-flow cell Zn anode mixture. In an embodiment, ZnO may be present inthe non-flow cell Zn anode mixture in an amount of about 10 wt. %, basedon the total weight of the non-flow cell Zn anode mixture. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the purpose of the ZnO in the non-flow cell Zn anode mixtureis to provide a source of Zn during the recharging steps.

In an embodiment, the electronically conductive material may be presentin the non-flow cell Zn anode mixture in an amount of from about 5 wt. %to about 20 wt. %, alternatively from about 5 wt. % to about 15 wt. %,or alternatively from about 5 wt. % to about 10 wt. %, based on thetotal weight of the non-flow cell Zn anode mixture. In an embodiment,the electronically conductive material may be present in the non-flowcell Zn anode mixture in an amount of about 10 wt. %, based on the totalweight of the non-flow cell Zn anode mixture. As will be appreciated byone of skill in the art, and with the help of this disclosure, theelectronically conductive material is used in the non-flow cell Zn anodemixture as a conducting agent, e.g., to enhance the overall electronicconductivity of the non-flow cell Zn anode mixture.

Nonlimiting examples of electronically conductive material suitable foruse in in this disclosure include carbon, graphite, graphite powder,graphite powder flakes, graphite powder spheroids, carbon black,activated carbon, conductive carbon, amorphous carbon, glassy carbon,and the like, or combinations thereof.

In an embodiment, the electronically conductive material suitable foruse in this disclosure comprises a graphite powder having a particlesize of from about 10 microns to about 95 microns, alternatively fromabout 15 microns to about 90 microns, or alternatively from about 17microns to about 85 microns.

In an embodiment, the electronically conductive material suitable foruse in this disclosure comprises a graphite powder having a specificBrunauer-Emmett-Teller (BET) area of from about 5 m²/g to about 30 m²/g,alternatively from about 6 m²/g to about 29 m²/g, or alternatively fromabout 7 m²/g to about 28 m²/g. The specific BET area is generallymeasured by adsorption using a BET isotherm, and this type ofmeasurement has the advantage of measuring surface of fine structuresand deep texture on particles.

Generally, a binder functions to hold the electroactive materialparticles (e.g., Zn used in anode, MnO₂ used in a cathode, etc.)together and in contact with the current collector. In an embodiment,the binder may be present in the non-flow cell Zn anode mixture in anamount of from about 2 wt. % to about 10 wt. %, alternatively from about2 wt. % to about 7 wt. %, or alternatively from about 4 wt. % to about 6wt. %, based on the total weight of the non-flow cell Zn anode mixture.In an embodiment, the binder may be present in the non-flow cell Znanode mixture in an amount of about 5 wt. %, based on the total weightof the non-flow cell Zn anode mixture.

In an embodiment, the binder may comprise a polymer; a fluoropolymer,polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene andpropylene; polyvinylidene fluoride (PVDF), a copolymer of styrene andbutadiene, styrene-butadiene rubber (SBR); a conducting polymer,polyaniline, polypyrrole, poly(3,4-ethylenedioxylthiophene) (PEDOT),copolymers of 3,4-ethylenedioxylthiophene with various co-monomers(e.g., PEDOT with various dopants), a copolymer of3,4-ethylenedioxylthiophene and styrenesulfonate (PEDOT:PSS), polyvinylalcohol (PVA), hydroxymethyl cellulose (HMC), carboxymethyl cellulose(CMC), and the like, or combinations thereof. In an embodiment, thebinder used in a non-flow cell Zn anode mixture comprises TEFLON, whichis a PTFE commercially available from DuPont.

In an embodiment the binder comprises a binder emulsion, wherein theconcentration of the solids in the binder emulsion may be from about 1wt. % to about 7 wt. %, alternatively from about 2 wt. % to about 6 wt.%, alternatively from about 3 wt. % to about 5 wt. %, based on the totalweight of the binder emulsion. As will be appreciated by one of skill inthe art, and with the help of this disclosure, the use of an emulsion asa binder reduces the amount of the binder available in the non-flow cellZn anode mixture. For example, if the binder is present in an amount ofabout 5 wt. % in the non-flow cell Zn anode mixture, and the binder usedis a 50 wt. % binder emulsion, the amount of binder in the binder isactually 2.5 wt. % (as opposed to 5 wt. %).

In an embodiment, the non-flow cell Zn anode mixture may be optionallyfiltered before any further processing, to ensure that no large clumpsof material are present within the mixture, and that the composition ofthe non-flow cell Zn anode may be uniform.

In some embodiments, the current collector comprises a porous metalcollector further comprising a variety of collector configurations, suchas for example a metal conductive mesh, a metal conductive interwovenmesh, a metal conductive expanded mesh, a metal conductive screen, ametal conductive plate, a metal conductive foil, a metal conductiveperforated plate, a metal conductive perforated foil, a metal conductiveperforated sheet, a sintered porous metal conductive sheet, a sinteredmetal conductive foam, an expanded conductive metal, a perforatedconductive metal, and the like, or combinations thereof. Other porouscollector configurations of the current collector will be appreciated byone of skill in the art in light of this disclosure.

In other embodiments, the current collector comprises a metal collectorpocketed assembly, wherein different pockets of the assembly maycomprise various electrode materials (e.g., non-flow cell Zn anodematerials, MnO₂ cathode materials, etc.). Other current collectorconfigurations will be apparent to one of skill in the art, and with thehelp of this disclosure.

In an embodiment, the current collector may be characterized by athickness of from about 150 microns to about 350 microns, alternativelyfrom about 200 microns to about 320 microns, or alternatively from about270 microns to about 290 microns.

In an embodiment, the current collector comprises a current collectorsubstrate comprising graphite, carbon, a metal, an alloy, steel (e.g.,304, 316, 302, etc.), copper, nickel, silver, platinum, brass, orcombinations thereof. In an embodiment, the current collector mayfurther comprise a metal deposited (e.g., electroplated,electrodeposited, etc.) on the current collector substrate, such as forexample nickel, silver, cadmium, tin, lead, bismuth, or combinationsthereof. In an embodiment, the current collector comprises anickel-plated steel mesh, an expanded nickel-plated steel mesh sheet, orcombinations thereof.

In an embodiment, the current collector may further comprise a currentcollector tab. In such embodiment, the current collector tab maycomprise a metal, nickel, copper, steel, and the like, or combinationsthereof. Generally, the current collector tab provides a means ofconnecting the electrode (e.g., anode, Zn anode, non-flow cell Zn anode,flow-assisted cell Zn anode, cathode, MnO₂ cathode) to the electricalcircuit of the battery. In some embodiments, the current collector tabmay be connected to a current collector across an entire length of thecurrent collector. In other embodiments, the current collector tab maybe connected to a current collector across a fraction of the entirelength of the current collector, such as for example, across about 5% ofthe entire length of the current collector, alternatively across about10%, alternatively across about 20%, alternatively across about 30%,alternatively across about 40%, alternatively across about 50%,alternatively across about 60%, alternatively across about 70%,alternatively across about 80%, alternatively across about 90%,alternatively across about 95%, or alternatively across about 99%.

In an embodiment, the current collector tab is in electrical contactwith an outer surface of the electrode (e.g., anode, Zn anode, non-flowcell Zn anode, flow-assisted cell Zn anode, cathode, MnO₂ cathode). Inan embodiment, the current collector tab is in electrical contact withless than about 0.2% of an outer surface of the electrode (e.g., anode,Zn anode, non-flow cell Zn anode, flow-assisted cell Zn anode, cathode,MnO₂ cathode), alternatively less than about 0.5%, or alternatively lessthan about 1%.

In some embodiments, the current collector may be positioned in thecenter of the electrode (e.g., anode, Zn anode, non-flow cell Zn anode,flow-assisted cell Zn anode, cathode, MnO₂ cathode). In otherembodiments, the current collector may be positioned off-center withinthe electrode (e.g., anode, Zn anode, non-flow cell Zn anode,flow-assisted cell Zn anode, cathode, MnO₂ cathode).

In an embodiment, the non-flow cell Zn anode mixture may be furthermixed with a non-flow cell solvent to yield a non-flow cell Zn anode wetmixture. Nonlimiting examples of non-flow cell solvents suitable for usein the present disclosure include alcohol (e.g., isopropanol, propanol),ethers, and the like, or combinations thereof. In an embodiment, thenon-flow cell solvent suitable for mixing with the non-flow cell Znanode mixture comprises isopropanol.

In an embodiment, the non-flow cell Zn anode mixture and the non-flowcell solvent may be mixed by using any suitable methodology, such as forexample in blenders, mixers, wet mixers, dry mixers, ball mills,Attritor mills, Hockmeyer mills, etc. In an embodiment, the non-flowcell Zn anode mixture and the non-flow cell solvent may be mixed in wetand/or dry conditions. In an embodiment, the non-flow cell Zn anodemixture and the non-flow cell solvent may be mixed in a mass ratio ofnon-flow cell Zn anode mixture to non-flow cell solvent of from about4:1 to about 10:1, alternatively from about 5:1 to about 8:1, oralternatively from about 6:1 to about 7:1.

In an embodiment, the non-flow cell Zn anode wet mixture may beoptionally filtered before any further processing, to ensure that nolarge clumps of material are present within the mixture, and that thecomposition of the non-flow cell Zn anode may be uniform.

In an embodiment, the non-flow cell Zn anode wet mixture has a pastyconsistency, thereby forming a pasted non-flow cell Zn anode. In anembodiment, the non-flow cell Zn anode wet mixture may be rolled out asa non-flow cell Zn anode mixture sheet by using any suitablemethodology, such as for example spreading the wet mixture on a planarsurface, pouring the wet mixture in a template, rolling the wet mixturewith a rolling pin, roll casting, coating, tape-casting, spraydeposition, screen-printing, calendaring, iso-static pressing, uniaxialpressing, etc. In an embodiment, the non-flow cell Zn anode mixturesheet may be characterized by a thickness of from about 100 microns toabout 1,000 microns, alternatively from about 300 microns to about 700microns, or alternatively from about 400 microns to about 600 microns.

In an embodiment, the non-flow cell Zn anode mixture sheet may be dried(e.g., in an oven) at a temperature of from about 40° C. to about 80°C., alternatively from about 50° C. to about 70° C., or alternativelyfrom about 55° C. to about 65° C., to yield a non-flow cell Zn anodedried sheet. In an embodiment, the non-flow cell Zn anode mixture sheetmay be dried in an oven at a temperature of about 60° C. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, drying the non-flow cell Zn anode mixture sheet removes atleast a portion of the non-flow cell solvent from the mixture sheet.

In an embodiment, the non-flow cell Zn anode dried sheet may be pressedonto the current collector to yield the non-flow cell Zn anode. In anembodiment, the non-flow cell Zn anode dried sheet may be pressed ontothe current collector under high pressure, such as for example apressure of from about 3,000 psi to about 10,000 psi, alternativelyabout 5,000 psi to about 9,000 psi, or alternatively about 6,000 psi toabout 8,000 psi. In an embodiment, the non-flow cell Zn anode driedsheet may be pressed onto the current collector such that the non-flowcell Zn anode mixture is in electrical contact with at least a portionof an outer surface of the current collector, e.g., the non-flow cell Znanode mixture is in electrical contact with at least a first side of thecurrent collector.

Alternatively, in an embodiment, the non-flow cell Zn anode wet mixturemay be rolled out as a non-flow cell Zn anode mixture sheet directlyonto the onto the current collector, followed by drying as previouslydescribed herein, to yield the non-flow cell Zn anode. In suchembodiment, the rolling out of the non-flow cell Zn anode mixture sheetonto the current collector may be accomplished by using any suitablemethodology, such as for example calendaring, iso-static pressing,uniaxial pressing, etc.

In an embodiment, the non-flow cell Zn anode may be further wrapped inan electrode separator membrane, wherein the electrode separatormembrane may be heat sealed onto the non-flow cell Zn anode to yield anon-flow cell sealed Zn anode. In an embodiment, the electrode separatormembrane comprises a polymeric membrane, such as for example a sinteredpolymer film membrane, polyolefin membrane, a polyolefin nonwovenmembrane, a cellulose membrane, a cellophane, a battery-gradecellophane, a hydrophilically modified polyolefin membrane, and thelike, or combinations thereof. In an embodiment, the electrode separatormembrane used to seal the non-flow cell Zn anode comprises FS 2192 SGmembrane, which is a polyolefin nonwoven membrane commercially availablefrom Freudenberg, Germany. As will be appreciated by one of skill in theart, and with the help of this disclosure, the electrode separatormembrane allows the electrolyte, or at least a portion and/or componentthereof, to pass (e.g., cross, traverse, etc.) through the electrodeseparator membrane, to balance ionic flow and sustain the flow ofelectrons in the battery.

In an embodiment, the non-flow cell Zn anode can be characterized by athickness of from about 100 microns to about 1,000 microns,alternatively from about 150 microns to about 600 microns, oralternatively from about 300 microns to about 500 microns. In anembodiment, the non-flow cell Zn anode can be characterized by athickness of about 400 microns.

In an embodiment, the non-flow cell Zn anode can be a porous composite.In an embodiment, the non-flow cell Zn anode may be characterized by aporosity of from about 5 vol. % to about 90 vol. %, alternatively fromabout 10 vol. % to about 85 vol. %, alternatively from about 20 vol. %to about 80 vol. %, based on the total volume of the non-flow cell Znanode mixture of the non-flow cell Zn anode. Generally, the porosity ofa material (e.g., non-flow cell Zn anode mixture of the non-flow cell Znanode, MnO₂ cathode mixture of the MnO₂ cathode, etc.) is defined as thepercentage of volume that pores (i.e., voids, empty spaces) occupy basedon the total volume of the material. As will be appreciated by one ofskill in the art, and with the help of this disclosure, an electrode(e.g., non-flow cell Zn anode, MnO₂ cathode, etc.) is porous such thatthe electrolyte solution (e.g., non-flow cell electrolyte solution,flow-assisted cell electrolyte solution) can permeate into at least aportion of the pore volume in the electrode (e.g., non-flow cell Znanode, MnO₂ cathode, etc.) and provide ionic communication to thesurrounding active material (e.g., Zn, MnO₂, etc.).

Referring to the embodiment of FIG. 2, a freestanding, self-supportedMnO₂ cathode 100 is depicted. The MnO₂ cathode 100 comprises a MnO₂cathode mixture 2 surrounding a current collector 1. The currentcollector is connected to a current collector tab 3. Without wishing tobe limited by theory, MnO₂ as part of the MnO₂ cathode mixture 2 is anelectrochemically active material that may participate in a redoxreaction (according to the reactions depicted in FIG. 1), therebycontributing to the overall voltage of the battery. The currentcollector 1 has the purpose of conducting current by enabling electronflow and does not significantly contribute to the overall voltage of thebattery. As will be appreciated by one of skill in the art, and with thehelp of this disclosure, the current collector 1 described as part ofthe non-flow cell Zn anode may also be used as the current collector forthe MnO₂ cathode 100. Further, as will be appreciated by one of skill inthe art, and with the help of this disclosure, the non-flow cell Znanode and the MnO₂ cathode do not share the same current collector, buta separate/distinct current collector is used for each electrode (e.g.,non-flow cell Zn anode, MnO₂ cathode).

In an embodiment, the MnO2 cathode mixture 2 comprises MnO2, anelectronically conductive material, and a binder. As will be appreciatedby one of skill in the art, and with the help of this disclosure, thebinder described as part of the non-flow cell Zn anode mixture may alsobe used as the binder for the MnO2 cathode mixture. In an embodiment,the binder used in a MnO2 cathode mixture comprises TEFLON. In analternative embodiment, the binder used in a MnO2 cathode mixturecomprises TEFLON, PEDOT, PSS, PEDOT:PSS, and/or any combination thereof.

In an embodiment, the binder may be present in MnO₂ cathode mixture inan amount of from about 2 wt. % to about 10 wt. %, alternatively fromabout 3 wt. % to about 7 wt. %, or alternatively from about 4 wt. % toabout 6 wt. %, based on the total weight of the MnO₂ cathode mixture. Inan embodiment, the binder may be present in the MnO₂ cathode mixture inan amount of about 5 wt. %, based on the total weight of MnO₂ cathodemixture. In an embodiment the binder comprises a binder emulsion,wherein the concentration of the solids in the binder emulsion may befrom about 1 wt. % to about 6 wt. %, alternatively from about 2 wt. % toabout 5 wt. %, alternatively from about 3 wt. % to about 5 wt. %, basedon the total weight of the binder emulsion. As will be appreciated byone of skill in the art, and with the help of this disclosure, the useof an emulsion as a binder reduces the amount of the binder available inthe MnO₂ cathode mixture. For example, if the binder is present in anamount of about 5 wt. % in the MnO₂ cathode mixture, and the binder usedis a 50 wt. % binder emulsion, the amount of binder in the binder isactually 2.5 wt. % (as opposed to 5 wt. %).

In an embodiment, the MnO₂ comprises electrolytic manganese dioxide(EMD) grade powder. In an embodiment, the MnO₂ has a powder particlesize distribution of equal to or greater than 99.5 wt. % MnO₂ powderparticles having a maximum size of about 100 mesh (based on U.S. SieveSeries, wet testing). In an embodiment, the MnO₂ has a powder particlesize distribution of from about 85 wt. % to about 95 wt. % MnO₂ powderparticles having a maximum size of about 200 mesh (based on U.S. SieveSeries, wet testing). In an embodiment, the MnO₂ has a powder particlesize distribution of equal to or greater than 60 wt. % MnO₂ powderparticles having a maximum size of about 325 mesh (based on U.S. SieveSeries, wet testing).

In an embodiment, MnO₂ may be present in the MnO₂ cathode mixture in anamount of from about 45 wt. % to about 80 wt. %, alternatively fromabout 55 wt. % to about 75 wt. %, or alternatively from about 60 wt. %to about 70 wt. %, based on the total weight of the MnO₂ cathodemixture. In an embodiment, MnO₂ may be present in the MnO₂ cathodemixture in an amount of about 65 wt. %, based on the total weight of theMnO₂ cathode mixture.

In an embodiment, the electronically conductive material may be presentin the MnO₂ cathode mixture in an amount of from about 10 wt. % to about45 wt. %, alternatively from about 20 wt. % to about 40 wt. %, oralternatively from about 25 wt. % to about 35 wt. %, based on the totalweight of the MnO₂ cathode mixture. In an embodiment, the electronicallyconductive material may be present in the MnO₂ cathode mixture in anamount of about 30 wt. %, based on the total weight of the MnO₂ cathodemixture. As will be appreciated by one of skill in the art, and with thehelp of this disclosure, MnO₂ has low electronic or electricalconductivity, hence the electronically conductive material is used inthe MnO₂ cathode mixture as a conducting agent, e.g., to enhance theoverall electronic conductivity of the MnO₂ cathode mixture. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the electronically conductive material described as part ofthe non-flow cell Zn anode mixture may also be used as theelectronically conductive material for the MnO₂ cathode mixture.

In an embodiment, the MnO₂ cathode mixture may further compriseadditives, such as for example metals, Bi, Sr, Ca, Ba, oxides thereof,hydroxides thereof, nitrates thereof, chlorides thereof, and the like,or combinations thereof.

In an embodiment, the MnO₂ cathode mixture may be optionally filteredbefore any further processing, to ensure that no large clumps ofmaterial are present within the mixture, and that the composition of theMnO₂ cathode may be uniform.

In an embodiment, the MnO₂ cathode mixture may be further mixed with anon-flow cell solvent to yield a MnO₂ cathode wet mixture. As will beappreciated by one of skill in the art, and with the help of thisdisclosure, the non-flow cell solvent described as part of a non-flowcell Zn anode assembly process may also be used as part of a MnO₂cathode assembly process. In an embodiment, the non-flow cell solventsuitable for mixing with the MnO₂ cathode mixture comprises isopropanol.

In an embodiment, the MnO₂ cathode mixture and the non-flow cell anodesolvent may be mixed by using any suitable methodology, such as forexample in blenders, mixers, wet mixers, dry mixers, ball mills,Attritor mills, Hockmeyer mills, etc. In an embodiment, the non-flowcell Zn anode mixture and the non-flow cell solvent may be mixed in wetand/or dry conditions. In an embodiment, the MnO₂ cathode mixture andthe non-flow cell anode solvent may be mixed in a mass ratio of MnO₂cathode mixture to non-flow cell anode solvent of from about 7:1 toabout 3:1, alternatively from about 5:1 to about 2:1, or alternativelyfrom about 5:1 to about 4:1.

In an embodiment, the MnO₂ cathode wet mixture may display a shearthinning behavior, e.g., the MnO₂ cathode wet mixture is a thixotropic(i.e., shear thinning) fluid, wherein the apparent viscosity of thefluid decreases with increased stress/shear. In an embodiment, the MnO₂cathode wet mixture has a pasty consistency, thereby allowing for theformation of a pasted MnO₂ cathode.

In an embodiment, the MnO₂ cathode wet mixture may be optionallyfiltered before any further processing, to ensure that no large clumpsof material are present within the mixture, and that the composition ofthe MnO₂ cathode may be uniform.

In an embodiment, the MnO₂ cathode wet mixture may be rolled out as aMnO₂ cathode mixture sheet by using any suitable methodology, such asfor example spreading the wet mixture on a planar surface, pouring thewet mixture in a template, rolling the wet mixture with a rolling pin,roll casting, coating, tape-casting, spray deposition, screen-printing,calendaring, iso-static pressing, uniaxial pressing, etc. In anembodiment, the MnO₂ cathode mixture sheet may be characterized by athickness of from about 100 microns to about 1,000 microns,alternatively from about 150 microns to about 600 microns, oralternatively from about 300 microns to about 500 microns.

In an embodiment, the MnO₂ cathode mixture sheet may be dried (e.g., inan oven) at a temperature of from about 40° C. to about 80° C.,alternatively from about 50° C. to about 70° C., or alternatively fromabout 55° C. to about 65° C., to yield a MnO₂ cathode dried sheet. In anembodiment, the non-flow cell Zn anode mixture sheet may be dried in anoven at a temperature of about 60° C. As will be appreciated by one ofskill in the art, and with the help of this disclosure, drying the MnO₂cathode mixture sheet removes at least a portion of the non-flow cellsolvent from the mixture sheet.

In an embodiment, the MnO₂ cathode dried sheet may be pressed onto thecurrent collector to yield the MnO₂ cathode. In an embodiment, the MnO₂cathode dried sheet may be pressed onto the current collector under highpressure, such as for example a pressure of from about 3,000 psi toabout 10,000 psi, alternatively about 5,000 psi to about 9,000 psi, oralternatively about 6,000 psi to about 8,000 psi. In an embodiment, theMnO₂ cathode dried sheet may be pressed onto the current collector suchthat the MnO₂ cathode mixture is in electrical contact with at least aportion of an outer surface of the current collector, e.g., the MnO₂cathode mixture is in electrical contact with at least a first side ofthe current collector.

In an embodiment, a first MnO₂ cathode dried sheet may be pressed onto afirst side of the current collector, and a second MnO₂ cathode driedsheet may be pressed onto a second side of the current collector toyield the MnO₂ cathode, such that the MnO₂ cathode mixture is inelectrical contact with both the first side and the second side of thecurrent collector. The MnO₂ cathode dried sheets (e.g., the first MnO₂cathode dried sheet, the second MnO₂ cathode dried sheet) may be pressedonto their respective sides of the current collector at the same time.Alternatively, the MnO₂ cathode dried sheets (e.g., the first MnO₂cathode dried sheet, the second MnO₂ cathode dried sheet) may be pressedonto their respective sides of the current collector at different times(e.g., sequentially).

In an alternative embodiment, the MnO₂ cathode wet mixture may be rolledout as a MnO₂ cathode mixture sheet directly onto the current collector,followed by drying as previously described herein, to yield the MnO₂cathode. In such embodiment, the rolling out of the MnO₂ cathode mixturesheet onto the current collector may be accomplished by using anysuitable methodology, such as for example calendaring, iso-staticpressing, uniaxial pressing, etc.

In an embodiment, the MnO₂ cathode may be further wrapped in at leastone electrode separator membrane, alternatively at least two electrodeseparator membranes, alternatively at least three electrode separatormembranes, alternatively at least four electrode separator membranes, oralternatively at least five electrode separator membranes, to yield asealed MnO₂ cathode. In an embodiment, the electrode separator membraneused to seal the MnO₂ cathode comprises cellophane. Further, as will beappreciated by one of skill in the art, and with the help of thisdisclosure, other numbers and configurations of electrode separatormembranes, depending on the desired battery design.

In an embodiment, the MnO₂ cathode may be a plate with flat surfaces,wherein the plate can be characterized by a thickness of from about 100microns to about 1,000 microns, alternatively from about 150 microns toabout 600 microns, or alternatively from about 300 microns to about 500microns. In an embodiment, the MnO₂ cathode can be characterized by athickness of about 400 microns.

In an embodiment, the MnO₂ cathode can be a porous composite. In anembodiment, the MnO₂ cathode may be characterized by a porosity of fromabout 5 vol. % to about 90 vol. %, alternatively from about 10 vol. % toabout 85 vol. %, alternatively from about 20 vol. % to about 80 vol. %,based on the total volume of the MnO₂ cathode mixture of the MnO₂cathode.

In an embodiment, the non-flow cell electrolyte solution comprises anion transporter such as for example an aqueous battery electrolyte or anaqueous electrolyte. In an embodiment, the aqueous battery electrolytecomprises any suitable aqueous electrolyte comprising ionic conductivityand with a pH value of about 14, alternatively less than about 14,alternatively less than about 13, or alternatively less than about 12.In the case of rechargeable batteries (e.g., secondary Zn—MnO₂batteries, non-flow secondary Zn—MnO₂ batteries, flow-assisted secondaryZn—MnO₂ batteries, etc.), the electrolyte is important both for theactive/discharging cycle of the battery (while the battery supplies acurrent) and for the recharging cycle when Zn may be electrodeposited toreplenish the anode material (e.g., Zn anode, non-flow cell Zn anode).

In an embodiment, the non-flow cell electrolyte solution comprises ahydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, andthe like, or combinations thereof, in a concentration of from about 1wt. % to about 50 wt. %, alternatively from about 10 wt. % to about 40wt. %, or alternatively from about 25 wt. % to about 35 wt. %, based onthe total weight of the non-flow cell electrolyte solution. In anembodiment, the non-flow cell electrolyte solution comprises potassiumhydroxide in a concentration of about 30 wt. %, based on the totalweight of the non-flow cell electrolyte solution.

In an embodiment, the non-flow secondary Zn—MnO₂ battery may beassembled by using any suitable methodology. In an embodiment, thenon-flow secondary Zn—MnO₂ battery may comprise at least one non-flowcell Zn anode and at least one MnO₂ cathode. In an embodiment, thenon-flow secondary Zn—MnO₂ battery may comprise more than one non-flowcell Zn anode and more than one MnO₂ cathode, wherein the anodes and thecathodes are assembled in an alternating configuration, e.g., the anodesand the cathodes are sandwiched together in an alternating manner. Forexample, if a non-flow secondary Zn—MnO₂ battery comprises two cathodesand three anodes, the electrodes would be sandwiched together in analternating manner: anode, cathode, anode, cathode, and anode. As willbe appreciated by one of skill in the art, and with the help of thisdisclosure, the number of electrodes in a non-flow secondary Zn—MnO₂battery is dependent upon the desired parameters for such secondaryZn—MnO₂ battery. In an embodiment, the number of electrodes (e.g.,non-flow cell Zn anode, MnO₂ cathode) in a non-flow secondary Zn—MnO₂battery may be chosen based on the size and properties of theelectrodes, such that anode and the cathode capacities may be at leastapproximately balanced.

In an embodiment, the non-flow secondary Zn—MnO₂ battery may beassembled by alternating a desired number of non-flow cell sealed Znanodes and a desired number of sealed MnO₂ cathode and holding theelectrodes along with the non-flow cell electrolyte solution undercompression in the non-flow battery housing.

In an embodiment, a method of producing energy may comprise the stepsof: (i) providing a non-flow secondary Zn—MnO₂ battery assembled asdisclosed herein, wherein the non-flow secondary Zn—MnO₂ battery may becharged when assembled; (ii) discharging the non-flow secondary Zn—MnO₂battery to a discharge voltage to produce energy, wherein at least aportion of the Zn of the non-flow cell Zn anode is oxidized; (iii)charging the flow-assisted secondary Zn—MnO₂ battery to a chargevoltage, wherein at least a portion of the ZnO from the non-flow cell Znanode mixture is reduced to Zn; and (iv) repeating the discharging andthe charging of the flow-assisted secondary Zn—MnO₂ battery.

Generally, the capacity of a given battery can be measured and expressedin terms of energy density, such as for example volumetric energydensity, which represents the ratio of energy available from a cell orbattery to its volume. The volumetric energy density is usuallyexpressed in watt-hours (energy) per liter (volume), written as Wh/L.Some factors that may affect the energy density (e.g., volumetric energydensity) of a given cell or battery may include the theoretical energyof the cell or battery which is dependent on the type, size and shape ofthe electrodes used, as well as on the type and concentration of theelectrolyte solution; the amount of inert material (as opposed toelectrochemically active material) including separators, binders, cans,air space, jackets, etc.; and the amount of electrochemically activematerial available to the cell or battery. In an embodiment, thenon-flow secondary Zn—MnO₂ battery may be characterized by a volumetricenergy density of equal to or greater than about 120 Wh/L, alternativelyequal to or greater than about 150 Wh/L, or alternatively equal to orgreater than about 200 Wh/L.

Generally, the current density of an electrode or a system of electrodesrefers to the amount of current that passes through such electrode orelectrode system per unit surface area of electrode(s). The currentdensity is usually expressed in A/cm². Similarly to the factors thataffect energy density, some factors that might affect current densityinclude the type of redox chemistry that occurs at the electrodes; theamount of inert material (as opposed to electrochemically activematerial) including separators, binders, cans, air space, jackets, etc.;the amount of electrochemically active material available to the cell orbattery; and the size and shape of the electrodes used, as this relatedto the surface area. In an embodiment, the non-flow secondary Zn—MnO₂battery may be characterized by a current density of from about 180A/cm² to about 300 A/cm², alternatively from about 190 A/cm² to about290 A/cm², or alternatively from about 200 A/cm² to about 280 A/cm².

Generally, the cycle life refers to the number of discharge-chargecycles a cell or battery can experience before it fails to meet specificperformance criteria. In an embodiment, the performance criteria maycomprise a discharge voltage or current over a specified time, which mayor may not be specified for a given number of discharge cycles. In anembodiment, the non-flow secondary Zn—MnO₂ battery may be characterizedby a cycle life of equal to or greater than about 5,000 cycles,alternatively equal to or greater than about 9,000 cycles, oralternatively equal to or greater than about 10,000 cycles.

In an embodiment, the non-flow secondary Zn—MnO₂ battery may be used attemperatures ranging from about −10° C. to about 65° C., alternativelyfrom about −5° C. to about 65° C., or alternatively from about 0° C. toabout 65° C.

Flow-Assisted Secondary Zn—MnO₂ Battery

In an embodiment, the secondary Zn—MnO₂ battery comprises aflow-assisted secondary Zn—MnO₂ battery. In this configuration, theelectrolyte is configured to freely flow between the Zn and MnO₂electrodes. In an embodiment, the flow-assisted secondary Zn—MnO₂battery comprises a flow-assisted battery housing, a flow-assisted cellZn anode, a MnO₂ cathode, and a flow-assisted cell electrolyte solution,where the flow-assisted cell Zn anode, the MnO₂ cathode, and theflow-assisted cell electrolyte solution may be located inside theflow-assisted battery housing.

The flow-assisted battery housing is configured to contain the flowassisted anodes, the flow assisted cell electrolyte solution and providefor a flow path for the circulation of the flow assisted cellelectrolyte solution. In an embodiment, the flow-assisted batteryhousing comprises a molded box or container that is generallynon-reactive with respect to the flow assisted cell electrolytesolution. In an embodiment, the flow assisted batter housing comprises apolypropylene molded box, an acrylic polymer molded box, or the like.

As will be appreciated by one of skill in the art, and with the help ofthis disclosure, the MnO₂ cathode described as part of the non-flowsecondary Zn—MnO₂ battery may also be used as the MnO₂ cathode for theflow-assisted secondary Zn—MnO₂ battery. In an embodiment, theflow-assisted secondary Zn—MnO₂ battery comprises a freestanding,self-supported MnO₂ cathode. In an embodiment, the flow-assistedsecondary Zn—MnO₂ battery comprises a MnO₂ cathode having a plateconfiguration, wherein the cathode may have flat surfaces, therebyenabling a layered design of the flow-assisted secondary Zn—MnO₂battery.

In an embodiment, the flow-assisted cell electrolyte solution comprisesan ion transporter such as for example an aqueous battery electrolyte oran aqueous electrolyte. In an embodiment, the aqueous batteryelectrolyte comprises any suitable aqueous electrolyte with good ionicconductivity and with a pH value of about 14, alternatively less thanabout 14, alternatively less than about 13, or alternatively less thanabout 12. In the case of rechargeable batteries (e.g., secondary Zn—MnO₂batteries, non-flow secondary Zn—MnO₂ batteries, flow-assisted secondaryZn—MnO₂ batteries, etc.), the electrolyte is important both for theactive/discharging cycle of the battery (while the battery supplies acurrent) and for the recharging cycle when Zn may be electrodeposited toreplenish the anode material (e.g., Zn anode, flow-assisted cell Znanode).

In an embodiment, the flow-assisted cell electrolyte solution comprisesa hydroxide, (e.g., potassium hydroxide, sodium hydroxide, lithiumhydroxide, and the like) and zinc oxide (ZnO), wherein the hydroxide canbe present in a concentration of from about 1 wt. % to about 50 wt. %,alternatively from about 10 wt. % to about 40 wt. %, or alternativelyfrom about 25 wt. % to about 35 wt. %, based on the total weight of thenon-flow cell electrolyte solution; and the ZnO can be present in anamount of from about 0 g/L to about 200 g/L, alternatively from about 30g/L to about 100 g/L, or alternatively from about 50 g/L to about 80g/L. In an embodiment, the flow-assisted cell electrolyte solutioncomprises potassium hydroxide in a concentration of about 30 wt. %,based on the total weight of the non-flow cell electrolyte solution; andZnO in an amount of about 60 g/L. The amount of ZnO in the flow-assistedcell electrolyte solution may vary depending on the charge-dischargestate of the battery since the ZnO is generated by the discharge of thebattery and consumed during the electrodeposition of Zn during therecharge cycle of the battery.

In an embodiment, the flow-assisted cell Zn anode compriseselectrodeposited Zn and a current collector, wherein the Zn can beelectrodeposited onto the current collector during the recharge cycle.While the present disclosure discusses the anodes in the context offlow-assisted cell zinc anodes, it should be understood that othermaterials, such as for example other metals, aluminum, nickel,magnesium, etc., may be used as flow-assisted cell anodes or anodematerials. Without wishing to be limited by theory, Zn as part of theflow-assisted cell Zn anode mixture is an electrochemically activematerial, and may participate in a redox reaction (according to thereactions depicted in FIG. 1), thereby contributing to the overallvoltage of the battery, while the current collector has the purpose ofconducting current by enabling electron flow and does not contribute tothe overall voltage of the battery. As will be appreciated by one ofskill in the art, and with the help of this disclosure, the currentcollector described as part of the non-flow secondary Zn—MnO₂ battery(e.g., part of the non-flow cell Zn anode, part of the MnO₂ cathode) mayalso be used as the current collector for the flow-assisted cell Znanode.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery may beassembled by using any suitable methodology. In an embodiment, theflow-assisted secondary Zn—MnO₂ battery may comprise at least oneflow-assisted cell Zn anode and at least one MnO₂ cathode. In anembodiment, the non-flow secondary Zn—MnO₂ battery may comprise morethan one flow-assisted cell Zn anode. As will be appreciated by one ofskill in the art, and with the help of this disclosure, the number ofelectrodes in a flow-assisted secondary Zn—MnO₂ battery is dependentupon the desired parameters for such secondary Zn—MnO₂ battery. In anembodiment, the number of electrodes (e.g., flow-assisted cell Zn anode,MnO₂ cathode) in a flow-assisted secondary Zn—MnO₂ battery can be chosenbased on the size and properties of the electrodes, such that anode andthe cathode capacities are balanced.

Referring to the embodiment of FIG. 3A, a top view of a flow-assistedsecondary Zn—MnO₂ battery 200 is shown. The electrodes are enclosed in aflow-assisted battery housing 50 which comprises at least two ports 30for circulating the flow-assisted cell electrolyte solution. In someembodiments, the flow-assisted battery housing 50 may not comprise anyports and an internal fluid circulation device such as a pump may beused to circulate the fluid within the flow-assisted battery housing 50.Two flow-assisted cell Zn anodes are located on inner surfaces of theflow-assisted battery housing 50, wherein the flow-assisted cell Znanodes face each other (e.g., the flow-assisted cell Zn anodes arelocated on inner surfaces of the flow-assisted battery housing 50 thatface each other or are diametrically opposed to each other). Theflow-assisted cell Zn anodes comprise a current collector 40 andelectrodeposited Zn 20. A MnO₂ cathode 10 is located in the middle ofthe flow-assisted battery housing 50, between the two flow-assisted cellZn anodes. While described as having the MnO₂ cathode 10 between the Znanodes, other configurations may also be possible.

Referring to the embodiment of FIG. 3B, a side view schematic of theflow-assisted secondary Zn—MnO₂ battery 200 of FIG. 3A is shown. Theflow-assisted cell Zn anodes comprising a current collector 40 andelectrodeposited Zn 20 are also visible in FIG. 3B, along with the MnO₂cathode 10. The side view schematic of FIG. 3B also shows both ports 30which allow for the flow-assisted cell electrolyte solution to becirculated, according to the electrolyte flow arrows 31, wherein a firstport (e.g., inlet port) is located in a lower region of theflow-assisted battery housing and a second port (e.g., outlet port) islocated in an upper region of the flow-assisted battery housing. Thisconfiguration of ports in the flow-assisted battery housing could ensurea vertical flow of flow-assisted cell electrolyte solution betweenadjacent electrodes (e.g., flow-assisted cell Zn anode, MnO₂ cathode).In an alternative embodiment, the first port located in the lower regionof the flow-assisted battery housing could be the outlet port and thesecond port located in the upper region of the flow-assisted batteryhousing could be the inlet port.

In an embodiment, a means for circulating the flow-assisted cellelectrolyte solution comprises a pump, which pumps the flow-assistedcell electrolyte solution through the flow-assisted battery housing(e.g., through the ports in the flow-assisted battery housing). As willbe appreciated by one of skill in the art, and with the help of thisdisclosure, alternative methods could be utilized for circulating the eflow-assisted cell electrolyte solution between the positive andnegative electrodes (e.g., flow-assisted cell Zn anode, MnO₂ cathode).For example, an internal stirrer or mixer could be provided within theflow-assisted battery housing and an external drive shaft could bemechanically coupled to the stirrer or mixer to rotate same in order tocirculate the flow-assisted cell electrolyte solution.

In an embodiment, one or more spacers could be used to physicallyseparate the electrodes (e.g., flow-assisted cell Zn anode, MnO₂cathode) in the flow-assisted secondary Zn—MnO₂ battery. In anembodiment, the spacers may comprise materials which (i) are chemicallystable in the flow-assisted cell electrolyte solution which is caustic(e.g., has a pH value of about 14) and (ii) have high electricalresistance. Nonlimiting examples of materials suitable for use in thespacers include nylon, acrylonitrile-butadiene-styrene copolymers (ABS),PTFE, acrylic polymers, polyolefins, and the like.

In an embodiment, the spacers comprise spacer washers, spacer bars, tierods, etc. In an embodiment, the spacer washers could be fixed to one orboth of the positive and negative electrodes (e.g., flow-assisted cellZn anode, MnO₂ cathode) and the respective electrodes could be formedwith through-holes that could be aligned with the through-holes of thewashers. In an embodiment, the spacer washers may have a thicknessmatching the desired spacing between adjacent electrodes (e.g.,flow-assisted cell Zn anode, MnO₂ cathode), and the spacer washers couldbe affixed to surfaces of the electrodes (e.g., flow-assisted cell Znanode, MnO₂ cathode) such that each pair of adjacent electrodes would bespaced from each other by the thickness of one spacer washer.

In an embodiment, each electrode (e.g., flow-assisted cell Zn anode,MnO₂ cathode) may have a matching pattern of spacer washers andthrough-holes such that when the electrodes (e.g., flow-assisted cell Znanode, MnO₂ cathode) are stacked within the flow-assisted batteryhousing, the spacer washers and through-holes of all the electrodeswould be aligned. In such embodiment, the tie rods could be insertedthrough the through-holes to assemble an electrode stack and keep theelectrodes (e.g., flow-assisted cell Zn anode, MnO₂ cathode) alignedwithin the flow-assisted battery housing. In an embodiment, the tie rodscould also be configured/used to support the electrode stack within theflow-assisted battery housing. For example, an inner surface of theflow-assisted battery housing could be formed with a lip or protrusion,wherein a row of tie rods could be seated on the lip to support theentire electrode stack within the flow-assisted battery housing.

In an alternative embodiment, the spacers could be arranged in a “windowframe” configuration, wherein a series of longitudinal spacer bars couldbe fixed in a vertical, parallel relationship to one or both of thepositive and negative electrodes (e.g., flow-assisted cell Zn anode,MnO₂ cathode). The spacer bars could be laterally spaced from each otherto form vertical parallel flow channels between adjacent electrodes(e.g., flow-assisted cell Zn anode, MnO₂ cathode).

In another embodiment, the spacers could be arranged in a serpentineconfiguration, wherein a continuous serpentine flow channel could beformed between adjacent electrodes (e.g., flow-assisted cell Zn anode,MnO₂ cathode). In such embodiment, vertical spacer bars having a lengthshorter than a length of their adjacent electrode would connect tohorizontal spacer bars to block the ends of the flow channels formed bythe vertical spacer bars. As a result, a continuous serpentine flow pathcould be created beginning at one corner of the electrode (e.g.,flow-assisted cell Zn anode, MnO₂ cathode) and terminating at anopposite corner.

In yet another embodiment, the electrodes (e.g., flow-assisted cell Znanode, MnO₂ cathode) comprise spacers in the form of insulatingprotuberances, wherein the insulating protuberances could be ininsulating spheres, which are press-fit, for example in apertures formedin the electrode (e.g., flow-assisted cell Zn anode, MnO₂ cathode). Insuch embodiment, a design of the spacers could determine a flow patternand characteristics of the flow-assisted cell electrolyte solution.Nonlimiting examples of flow patterns that could be created by usingvarious spacer designs include serpentine flow, linear flow between theelectrodes, series/parallel flow combinations between the electrodes,etc.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery mayfurther comprise a catalytic plate disposed at the bottom of theflow-assisted battery housing, wherein the catalytic plate may collectisolated zinc falling from the flow-assisted cell Zn anode. Thecatalytic plate may comprise pure nickel metal, nickel coated steel, orsteel coated with small amounts of catalysts intended to promotehydrogen evolution. Without wishing to be limited by theory, when theisolated zinc falls and rests on the catalytic plate, a local corrosioncell is created, with the net effect of hydrogen evolution occurring onthe plate, and corrosion and dissolution of the isolated zinc. In anembodiment, the catalytic plate may remove at least a portion of themetallic zinc which has become detached by any reason from theflow-assisted cell Zn anode. In an embodiment, the catalytic plate mayremove all of the metallic zinc which has become detached by any reasonfrom the flow-assisted cell Zn anode. In an alternative embodiment, thecatalytic plate may be electrically connected to the MnO₂ cathode,thereby readily dissolving any metallic zinc solids reaching thecatalytic plate.

In an embodiment, during a cycle of operation of the flow-assistedsecondary Zn—MnO₂ battery the ZnO of the flow-assisted cell electrolytesolution can be deposited as metallic Zn on the current collectors ofthe flow-assisted cell Zn anodes during charging. As the flow-assistedsecondary Zn—MnO₂ battery discharges in use, the metallic zinc depositedon the current collectors of the flow-assisted cell Zn anodes can beoxidized to form a zinc oxide, which then dissolves back into theflow-assisted cell electrolyte solution.

In an embodiment, the flow-assisted cell electrolyte solution may becontinuously circulated through the flow-assisted battery housing aspreviously described herein, thereby keeping the flow-assisted cellelectrolyte solution well stirred and ensuring an even, homogenousmixture and temperature of the flow-assisted cell electrolyte solution.Without wishing to be limited by theory, the concentration of zincspecies (e.g., ZnO) in the flow-assisted cell electrolyte solutiondecreases during charging of the flow-assisted secondary Zn—MnO₂battery, and the continuous circulation of the flow-assisted cellelectrolyte solution maintains the concentration of the zinc speciesuniform throughout the solution, thereby minimizing Zn dendriteformation and ensuring an uniform deposition of Zn onto theflow-assisted cell Zn anode.

In an embodiment, continuous circulation of the flow-assisted cellelectrolyte solution through the flow-assisted battery housing may allowcomplete dissolution of all Zn from the flow-assisted cell Zn anodeduring discharge. In such embodiment, the flow-assisted secondaryZn—MnO₂ battery can be subjected to a reconditioning cycle, wherein allZn could be dissolved/removed from the flow-assisted cell Zn anode,thereby allowing the flow-assisted cell Zn anode to return to itsoriginal condition (e.g., condition prior to utilizing the flow-assistedsecondary Zn—MnO₂ battery). In an embodiment, the reconditioning cyclecan be performed periodically during a life of the flow-assistedsecondary Zn—MnO₂ battery to improve performance of the battery andlengthen the life of the battery. In an embodiment, the reconditioningcycle can be performed at least every 20 charge/discharge cycles,alternatively at least 25 charge/discharge cycles, or alternatively atleast 30 charge/discharge cycles.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery could beoperated as a closed-loop system, wherein any gases evolved from theelectrodes (oxygen from the MnO₂ cathode and hydrogen from theflow-assisted cell Zn anode) may be recombined to form water, therebyensuring a constant water inventory in the flow-assisted secondaryZn—MnO₂ battery over its life. In an embodiment, small pieces ofcatalyst could be placed within electrolyte-free headspace of theflow-assisted secondary Zn—MnO₂ battery, thereby reducing the pressureduring closed-loop operation. Without wishing to be limited by theory,the pressure reduction is due to the recombining of hydrogen and oxygengenerated during the operation of the flow-assisted secondary Zn—MnO₂battery.

In an embodiment, a method of producing energy may comprise the stepsof: (i) providing a flow-assisted secondary Zn—MnO₂ battery assembled asdisclosed herein; (ii) charging the flow-assisted secondary Zn—MnO₂battery to a charge voltage, wherein ZnO from the flow-assisted cellelectrolyte solution is deposited as electrodeposited Zn on the currentcollector of the flow-assisted cell Zn anode; (iii) discharging theflow-assisted secondary Zn—MnO₂ battery to a discharge voltage toproduce energy, wherein at least a portion of the electrodeposited Zn ofthe flow-assisted cell Zn anode is oxidized and transferred back intothe flow-assisted cell electrolyte solution; (iv) optionally furtherdischarging the flow-assisted secondary Zn—MnO₂ battery to a finalvoltage below said discharge voltage, wherein the electrodeposited Zn ofthe flow-assisted cell Zn anode is completely removed from theflow-assisted cell Zn anode; and (v) continuously circulating theflow-assisted cell electrolyte solution through the flow-assistedbattery housing during said steps of charging, discharging and furtherdischarging the flow-assisted secondary Zn—MnO₂ battery to said finalvoltage, wherein the electrodeposited Zn is stripped and re-deposited onthe current collector of the flow-assisted cell Zn anode.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery may becharacterized by a volumetric energy density of equal to or greater thanabout 60 Wh/L, alternatively equal to or greater than about 50 Wh/L, oralternatively equal to or greater than about 40 Wh/L.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery may becharacterized by a current density of from about 0.01 A/cm² to about 0.1A/cm², alternatively from about 0.01 A/cm² to about 0.03 A/cm², oralternatively from about 0.01 A/cm² to about 0.02 A/cm².

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery may becharacterized by a cycle life of equal to or greater than about 200cycles, alternatively equal to or greater than about 250 cycles, oralternatively equal to or greater than about 300 cycles.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery may beused at temperatures ranging from about 5° C. to about 65° C.,alternatively from about 10° C. to about 65° C., or alternatively fromabout 15° C. to about 65° C.

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery) andmethods of using the same disclosed herein may advantageously displayimproved stability, performance, and/or other desired attributes orcharacteristics. Generally, the devices that are used to storeelectrical energy are required to be safe, environmentally benign,cheap, and reliable, offering many years of maintenance-freeperformance. The secondary Zn—MnO₂ batteries (e.g., non-flow secondaryZn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery) disclosedherein convey a new approach to the design, manufacturing, andapplication of a well-established electrochemical system (e.g., Zn—MnO₂)to a novel secondary or rechargeable battery which can offer high cyclelife; cheap construction cost; safe, non-flammable electrolyte solution(e.g., non-flow cell electrolyte solution, flow-assisted cellelectrolyte solution); and maintenance-free operation, while providinghigh-capacity and high power delivery of electrical energy. Withoutwishing to be limited by theory, the secondary Zn—MnO₂ batteries (e.g.,non-flow secondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂battery) disclosed herein have a great power capability due to the fastkinetics of the electrodes (e.g., non-flow cell Zn anode, flow-assistedcell Zn anode, MnO₂ cathode) and low resistance of the electrolytesolution (e.g., non-flow cell electrolyte solution, flow-assisted cellelectrolyte solution).

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously display the characteristics of beingan inexpensive, rechargeable battery with improved cycle life and highvolumetric energy density, improved performance at high currentdensities; and using environmentally friendly materials as theelectroactive electrode materials. With these advantages, the secondaryZn—MnO₂ batteries (e.g., non-flow secondary Zn—MnO₂ battery,flow-assisted secondary Zn—MnO₂ battery) have high potential to replacelead-acid and nickel-cadmium batteries in high power applications, suchas automotive starter batteries (ASB) and uninterrupted power back-upsystems (UPS). For instance, in automobiles when the engine is turnedon, high power is required, typically 300 A at 12 V for a fraction of asecond, which may be repeated a few times. Also for UPS applications,high power is required when the input power supply fails while handlinghigh frequency transient loads. Currently-used lead-acid batteries arenot only made of hazardous materials such as lead and acid electrolyte,but they also have low volumetric energy densities (e.g., 50-60 Wh/L),limited lifetimes when deeply discharged or used repeatedly in highdrain (power) situations. However, of the currently available batterytechnologies, only lead-acid offers both a price point that iscommensurate with these types of applications and safe operation(relative to Li-ion or Na—S technology).

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously comprise a pasted configuration,wherein at least one electrode comprises a pasted electrode, such as forexample a pasted non-flow cell Zn anode, a pasted MnO₂ cathode, etc. Insuch embodiment, the pasted configuration of the secondary Zn—MnO₂batteries (e.g., non-flow secondary Zn—MnO₂ battery, flow-assistedsecondary Zn—MnO₂ battery) may optimize the batteries for high powerapplications, such as for example vehicle starting and power protection.

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously supply high currents at very highcurrent densities. In such embodiment, given the advantageous low costand high power of the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein, these secondary Zn—MnO₂ batteries could be used asstarter batteries for vehicles or in UPS applications as low-cost andenvironmentally friendly direct replacements to currently used lead-acidbatteries. The non-flow secondary Zn—MnO₂ batteries disclosed herein canbe successfully cycled for more than 10,000 cycles with rapid chargingat high power cycling as a vehicle battery.

In an embodiment, the non-flow secondary Zn—MnO₂ battery disclosedherein may advantageously be already charged as assembled/manufactured,thereby requiring no additional processing and reducing manufacturingtime and space requirements for its production.

In an embodiment, the flow-assisted secondary Zn—MnO₂ battery disclosedherein may advantageously comprise freestanding MnO₂ cathodes affordedby continuously circulating the flow-assisted cell electrolyte solution,thereby eliminating the need for any additional supporting structures orgeometries.

In an embodiment, the cost of material needed in the secondary Zn—MnO₂batteries (e.g., non-flow secondary Zn—MnO₂ battery, flow-assistedsecondary Zn—MnO₂ battery) disclosed herein can advantageously be lessthan half the cost of materials for a lead-acid battery. The low cost ofsuch rechargeable, high power, long life secondary Zn—MnO₂ batteriesrenders the secondary Zn—MnO₂ batteries disclosed herein highly valuableand much desired.

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously display good ionic transport andhigh conductivity, which is required for high power applications toreduce polarization resistance, owing to the optimization of electrodecomposition and thickness, as well as electrolyte concentration. In anembodiment, small-scale secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery) mayadvantageously display excellent performance in terms of minimum voltagerequirement for starter batteries in vehicles, at high C-rates (3-4 Crates). Generally, a C-rate is a measure of the rate at which a cell orbattery is discharged relative to its maximum capacity. While describingbatteries, discharge current is often expressed as a C-rate in order tonormalize against battery capacity, since the battery capacity is oftenvery different between batteries. For example, a 1 C rate means that thedischarge current may discharge the entire battery in 1 hour.

In an embodiment, the secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously display multiple successful enginestarts in a vehicle. The secondary Zn—MnO₂ batteries (e.g., non-flowsecondary Zn—MnO₂ battery, flow-assisted secondary Zn—MnO₂ battery)disclosed herein may advantageously exhibit reserve energy twice as highas a comparable lead-acid battery. The secondary Zn—MnO₂ batteries(e.g., non-flow secondary Zn—MnO₂ battery, flow-assisted secondaryZn—MnO₂ battery) disclosed herein may also display excellent performanceat low temperatures (e.g., about 0° C.) and maintain voltage well above7.2 V as required for cold cranking currents as per SAE standards, whenused in vehicles. Additional advantages of the secondary Zn—MnO₂batteries (e.g., non-flow secondary Zn—MnO₂ battery, flow-assistedsecondary Zn—MnO₂ battery) and methods of using same may be apparent toone of skill in the art viewing this disclosure.

EXAMPLES

The embodiments having been generally described, the following examplesare given as particular embodiments of the disclosure and to demonstratethe practice and advantages thereof. It is understood that the examplesare given by way of illustration and are not intended to limit thespecification or the claims in any manner.

Example 1

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the viscosity behavior ofa MnO₂ cathode mixture; the effect of the thickness of the MnO₂ cathodeon discharge capacity were investigated.

A MnO₂ cathode mixture was prepared by blending for 2 minutes: 65 wt. %MnO₂, 35 wt. % graphite, and 5 wt. % TEFLON emulsion, wherein the TEFLONemulsion contained 60 wt. % TEFLON, followed by filtering the MnO₂cathode mixture. The viscosity behavior of the MnO₂ cathode mixture wasanalyzed by an ARES controlled strain rheometer, and the data isdisplayed in the graph of FIG. 4A. The MnO₂ cathode mixture clearlyshows a strong shear thinning behavior. For stresses below about 50 Pa,elastic behavior dominates viscous behavior. For stresses above about 50Pa, the dominant term is reversed, as shown in FIG. 4B.

Example 2

The MnO₂ cathode mixture described in Example 1 was used for preparingMnO₂ cathodes of three different thicknesses: 1 mm (0.039 inches), 0.6mm (0.024 inches), 0.4 mm (0.016 inches). The anode used in all casedwas a 0.4 mm (0.016 inches) thick non-flow cell Zn anode comprising 85wt. % Zn, 10 wt. % ZnO, and 5 wt. % TEFLON emulsion, wherein the TEFLONemulsion contained 60 wt. % TEFLON. The non-flow cell electrolytesolution was a 30 wt. % potassium hydroxide aqueous solution.

Non-flow secondary Zn—MnO₂ batteries were prepared by heat-sealing thenon-flow cell Zn anode in one layer of FS 2192 SG membrane as theelectrode separator membrane for the anode; wrapping the MnO₂ cathode in3 layers of battery-grade cellophane as the electrode separator membranefor the cathode; sandwiching alternately two MnO₂ cathodes and threenon-flow cell Zn anodes, followed by holding these electrodes undercompression in a polysulfone-molded box. A 30 wt. % potassium hydroxide(KOH) solution was used as the non-flow cell electrolyte solution.

The non-flow secondary Zn—MnO₂ batteries were tested at high C-rates (3C rate), and the data is displayed in the graph of FIG. 5. This C-rate(3 C rate) or current density is as needed for a vehicle starterbattery. Three high current pulses were given for 30 seconds each with 5seconds rests in between pulses. As shown in FIG. 5, with decreasingthickness of the MnO₂ cathode, the high rate performance increases. Forthinner MnO₂ cathodes, the accessible capacity increases. From FIG. 5,it is clear that reduced MnO₂ cathode thickness results in betterperformance of the non-flow secondary Zn—MnO₂ battery voltage. Thisvoltage of the non-flow secondary Zn—MnO₂ battery is above the minimumvoltage requirement for an alternator to operate in a vehicle if stringsof such batteries are connected in series.

Example 3

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the effect of thethickness of the electrode separator membrane of the MnO₂ cathode on theperformance of the non-flow secondary Zn—MnO₂ battery was investigated.

Non-flow secondary Zn—MnO₂ batteries were prepared as described inExample 2, with the difference that the number of layers of electrodeseparator membranes (e.g., battery-grade cellophane) of the MnO₂ cathodewas varied to obtain desired thicknesses of the electrode separatormembranes. The metric used to measure the performance of the non-flowsecondary Zn—MnO₂ batteries was the product of applied current andthickness of the electrode separator membrane at a given voltage, whichrepresents an indirect measure of the resistance across the electrodeseparator membrane, and the results are displayed in FIG. 6. As it canbe seen from the graph of FIG. 6, as the thickness of the electrodeseparator membrane of the MnO₂ cathode decreases, the ohmic drop acrossthe electrode separator membrane of the MnO₂ cathode decreases as well.

Example 4

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the effect of the currentcollector tab location as well as electrode size in non-flow secondaryZn—MnO₂ battery were investigated.

Non-flow secondary Zn—MnO₂ batteries were prepared as described inExample 2. The location of the current collector tab (CC tab) was variedaccording to the schematic in FIG. 7. In one configuration the currentcollector tab was located in the left corner of the current collectormesh (CC mesh) as part of the electrode. In another configuration, thecurrent collector tab was located on the left side along the entirelength of the current collector mesh (CC mesh) as part of the electrode.

The ohmic drop was measured in terms of the voltage drop at a givencurrent density. The pulse voltage drop was measured at given currentdensity for 10 seconds, and the data are displayed in FIG. 8. The twoelectrodes tested for the results displayed in FIG. 8A were the samesize: 5 cm×7.6 cm, and the data indicates that for small sizeelectrodes, the location of current collector tab is unimportant as thecurrent distribution is more uniform. However, the effect of electrodesize and current collector tab becomes more important at high currentdischarges. The two electrodes tested for the results displayed in FIG.8B were the same size (8.9 cm×11.4 cm), but larger than the electrodestested for the data in FIG. 8A. The data in FIG. 8B indicates that asthe size of the electrode increases, the location of the currentcollector tab plays an important role in the current distribution. Forlarger electrodes (e.g., 8.9 cm×11.4 cm) if the current collector tab isplaced along the entire length of the current collector mesh, the ohmicdrop is less, as shown in FIG. 8B.

Example 5

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the effect of theconcentration of hydroxide in the non-flow cell electrolyte solution ina non-flow secondary Zn—MnO₂ battery was investigated.

Non-flow secondary Zn—MnO₂ batteries were prepared as described inExample 2, with the difference that the concentration of potassiumhydroxide was varied: 10 wt. %, 30 wt. %, and 37 wt. %. The effect ofelectrolyte conductivity was studied by varying the concentration ofpotassium hydroxide in the non-flow cell electrolyte solution. The pulsevoltage drop was measured at a given current density for 10 seconds, andthe data are displayed in FIG. 9. FIG. 9 shows the effect of theconcentration of potassium hydroxide in the non-flow cell electrolytesolution at high rate discharges. As the conductivity increases, theohmic drop measured in terms of the pulse voltage drop decreases.

Example 6

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the effect of the binderof a MnO₂ cathode in non-flow secondary Zn—MnO₂ battery wasinvestigated.

A MnO₂ cathode mixture was prepared by blending 67 wt. % MnO₂, 28 wt. %graphite, 2 wt. % TEFLON, and 3 wt. % PEDOT:PSS for 2 minutes, followedby filtering the MnO₂ cathode mixture and rolling it into a MnO₂ cathodemixture sheet. This MnO₂ cathode mixture sheet was formed into a MnO₂cathode with a thickness of 0.6 mm (0.024 inches) by pressing the MnO₂cathode mixture sheet onto a Ni mesh current collector at 10,000 psi.This MnO₂ cathode was then used to make and test a non-flow secondaryZn—MnO₂ battery as described in Example 1. The results were plottedalong with the data displayed in FIG. 5 for comparison, and all theseresults are displayed in FIG. 10. The PEDOT:PSS was added to the MnO₂cathode mixture as a conductive binder. FIG. 10 shows the effect ofaddition of PEDOT:PSS on the high rate performance/high rate dischargecapacity of the non-flow secondary Zn—MnO₂ battery. At high rates ofdischarge, with the addition of conductive binder (PEDOT:PSS) theaccessible capacity increases with more MnO₂ loading (i.e., increasedthickness of the MnO₂ cathode).

Example 7

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the cycle life of anon-flow secondary Zn—MnO₂ battery was investigated.

A non-flow secondary Zn—MnO₂ battery was prepared as described inExample 2. Three high current pulses have been given and then thenon-flow secondary Zn—MnO₂ battery was charged. Such charge-dischargecycling was continued to study the cycle life of the non-flow secondaryZn—MnO₂ battery under typical vehicle engine starting conditions. FIG.11 clearly shows the excellent cycling performance over 10,000 startattempts with no significant deterioration of the active material in theelectrodes.

Example 8

The properties of a non-flow secondary Zn—MnO₂ battery and/or componentsthereof were investigated. More specifically, the discharge at differentC-rates for a non-flow secondary Zn—MnO₂ battery was investigated.

A non-flow secondary Zn—MnO₂ battery was prepared as described inExample 2, and the tests were conducted at 0° C., to assess theperformance of the non-flow secondary Zn—MnO₂ battery at lowtemperatures. As per SAE standards, the low temperature performance ofthe battery was tested at different C-rates until the battery voltagedropped to 7.2 V after 30 seconds, and the data is shown in FIG. 12. Thenon-flow secondary Zn—MnO₂ battery clearly shows good performance after30 seconds of discharge maintaining the required voltage (7.2 V).

Example 9

The properties of a MnO₂ cathode were investigated. More specifically,the structure of the MnO₂ cathode was investigated.

A MnO₂ cathode mixture was prepared by blending 65 wt. % MnO₂, 30 wt. %graphite, and 5 wt. % TEFLON for 2 minutes, followed by filtering theMnO₂ cathode mixture and rolling it into a MnO₂ cathode mixture sheet.This MnO₂ cathode mixture sheet was formed into a freestanding,self-supported MnO₂ cathode by pressing the MnO₂ cathode mixture sheetonto a Ni mesh current collector at 10,000 psi.

A scanning electron micrograph of a cross-section of the freestanding,self-supported MnO₂ cathode is shown in FIG. 13. The scanning electronmicrograph shows the position of the current collector 301 within thefreestanding, self-supported MnO₂ cathode, as well as the MnO₂ cathodemixture 302 surrounding a current collector 301.

Example 10

The properties of a flow-assisted secondary Zn—MnO₂ battery and/orcomponents thereof were investigated. More specifically, capacity andenergy efficiency of a flow-assisted secondary Zn—MnO₂ battery wereinvestigated.

A MnO₂ cathode mixture was prepared as described in Example 9. Aflow-assisted cell Zn anode comprising a Ni-plated Cu current collectorwas pre-deposited with a layer of Zn. The size of the flow-assisted cellZn anode was 2 inches×3 inches. The electrodes (cathode assembly andanode pair) were then placed in an acrylic flow-assisted battery housingflow cell, as shown in FIGS. 3A and 3B, with a MnO₂ cathode toflow-assisted cell Zn anode separation of 4 mm, to form theflow-assisted secondary Zn—MnO₂ battery. The flow-assisted cellelectrolyte solution contained 45 wt. % KOH and 60 mg/L ZnO, and theflow-assisted cell electrolyte solution was flowed past the electrodes(e.g., MnO₂ cathode, flow-assisted cell Zn anodes).

The performance of the flow-assisted secondary Zn—MnO₂ battery wasmeasured and the results are shown in FIGS. 14 and 15. FIG. 14 showscapacity as a function of cycle number, indicating that the cycle lifeof the flow-assisted secondary Zn—MnO₂ battery is at least about 200cycles. FIG. 15 shows coulombic and energy efficiency as a function ofcycle number for the flow-assisted secondary Zn—MnO₂ battery, stressingthat the cycle life of the flow-assisted secondary Zn—MnO₂ battery is atleast about 200 cycles.

ADDITIONAL DISCLOSURE

The following are nonlimiting, specific embodiments in accordance withthe present disclosure:

In a first embodiment, a secondary Zn—MnO₂ battery comprises a batteryhousing, a MnO₂ cathode, a Zn anode, and an electrolyte solution. TheMnO₂ cathode, the Zn anode, and the electrolyte solution are disposedwithin the battery housing, and the MnO₂ cathode comprises a MnO₂cathode mixture and a current collector. The MnO₂ cathode mixture is inelectrical contact with at least a portion of an outer surface of thecurrent collector, and the MnO₂ cathode has a porosity of from about 5vol. % to about 90 vol. %, based on the total volume of the MnO₂ cathodemixture of the MnO₂ cathode.

A second embodiment may include the secondary Zn—MnO₂ battery of thefirst embodiment, wherein the Zn anode and the MnO₂ cathode capacitiesmay be approximately balanced.

A third embodiment may include the secondary Zn—MnO₂ battery of thefirst or second embodiment, wherein at least one of the Zn anode or theMnO₂ cathode may comprise a pasted configuration.

A fourth embodiment may include the secondary Zn—MnO₂ battery of any ofthe first to third embodiments, wherein at least one of the MnO₂ cathodeor the Zn anode may have a thickness of from about 100 microns to about1,000 microns.

A fifth embodiment may include the secondary Zn—MnO₂ battery of any ofthe first to third embodiments, wherein at least one of the MnO₂ cathodeor the Zn anode may have a thickness of about 400 microns.

A sixth embodiment may include the secondary Zn—MnO₂ battery of any ofthe first to fifth embodiments, wherein at least one of the MnO₂ cathodeor the Zn anode may be further wrapped in an electrode separatormembrane.

A seventh embodiment may include the secondary Zn—MnO₂ battery of thesixth embodiment, wherein the electrode separator membrane comprises apolymeric membrane, a sintered polymer film membrane, a polyolefinmembrane, a polyolefin nonwoven membrane, a cellulose membrane, acellophane, a battery-grade cellophane, a sintered polyolefin filmmembrane, a hydrophilically modified polyolefin membrane, or anycombinations thereof.

An eighth embodiment may include the secondary Zn—MnO₂ battery of any ofany of the first to seventh embodiments, wherein the MnO₂ cathodemixture may comprise MnO₂ in an amount of from about 45 wt. % to about80 wt. %, an electronically conductive material in an amount of fromabout 10 wt. % to about 45 wt. %, and a binder in an amount of fromabout 2 wt. % to about 10 wt. %, based on a total weight of the MnO₂cathode mixture.

A ninth embodiment may include the secondary Zn—MnO₂ battery of theeighth embodiment, wherein the MnO₂ may comprise electrolytic manganesedioxide; wherein the electronically conductive material may comprisecarbon, graphite, graphite powder, graphite powder flakes, graphitepowder spheroids, carbon black, activated carbon, conductive carbon,amorphous carbon, glassy carbon, or any combination thereof; and whereinthe binder may comprise a polymer; a fluoropolymer,polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene andpropylene; polyvinylidene fluoride (PVDF), a copolymer of styrene andbutadiene, styrene-butadiene rubber (SBR); a conducting polymer,polyaniline, polypyrrole, poly(3,4-ethylenedioxylthiophene) (PEDOT),copolymers of 3,4-ethylenedioxylthiophene with various co-monomers(e.g., PEDOT with various dopants), a copolymer of3,4-ethylenedioxylthiophene and styrenesulfonate (PEDOT:PSS), polyvinylalcohol (PVA), hydroxymethyl cellulose (HMC), carboxymethyl cellulose(CMC), or any combination thereof.

A tenth embodiment may include the secondary Zn—MnO₂ battery of any ofany of the first to ninth embodiments, wherein the MnO₂ cathode mixturemay further comprise a metal, Bi, Sr, Ca, Ba, an oxide thereof, ahydroxides thereof, a nitrate thereof, a chlorides thereof, or anycombination thereof.

An eleventh embodiment may include the secondary Zn—MnO₂ battery of thefirst embodiment, wherein the MnO₂ cathode may comprise a pasted MnO₂cathode.

A twelfth embodiment may include the secondary Zn—MnO₂ battery of any ofthe first to eleventh embodiments, wherein the MnO₂ cathode may comprisea first MnO₂ cathode dried sheet, a second MnO₂ cathode dried sheet, andthe current collector, wherein the first MnO₂ cathode dried sheet may bepressed onto a first side of the current collector, wherein the secondMnO₂ cathode dried sheet may be pressed onto a second side of thecurrent collector, wherein the first and the second MnO₂ cathode driedsheets may be pressed onto their respective sides of the currentcollector at a pressure of from about 3,000 psi to about 10,000 psi, andwherein the MnO₂ cathode mixture may be in electrical contact with boththe first side and the second side of the current collector.

A thirteenth embodiment may include the secondary Zn—MnO₂ battery of anyof the first to twelfth embodiments, wherein the current collector maycomprise a porous metal collector, a metal conductive mesh, a metalconductive interwoven mesh, a metal conductive expanded mesh, a metalconductive screen, a metal conductive plate, a metal conductive foil, ametal conductive perforated plate, a metal conductive perforated foil, ametal conductive perforated sheet, a sintered porous metal conductivesheet, a sintered metal conductive foam, an expanded conductive metal, aperforated conductive metal, or any combination thereof.

A fourteenth embodiment may include the secondary Zn—MnO₂ battery of anyof the first to twelfth embodiments, wherein the current collectorcomprises a metal collector pocketed assembly.

A fifteenth embodiment may include the secondary Zn—MnO₂ battery of anyof the first to fourteenth embodiments, wherein the current collectormay comprise a current collector substrate comprising graphite, carbon,a metal, an alloy, steel, copper, nickel, silver, platinum, brass, orany combination thereof.

A sixteenth embodiment may include the secondary Zn—MnO₂ battery of thefifteenth embodiment, wherein the current collector may comprise ametal, nickel, silver, cadmium, tin, lead, bismuth, or any combinationsthereof deposited on the current collector substrate.

A seventeenth embodiment may include the secondary Zn—MnO₂ battery ofany of the first to sixteenth embodiments, wherein the current collectormay comprise a current collector tab, and wherein the current collectortab may be in electrical contact with an outer surface of the MnO₂cathode.

An eighteenth embodiment may include the secondary Zn—MnO₂ battery ofany of the first to seventeenth embodiments, wherein the secondaryZn—MnO₂ battery may comprise a non-flow secondary Zn—MnO₂ battery,wherein the battery housing may comprise a non-flow battery housing,wherein the Zn anode may comprise a non-flow cell Zn anode, and whereinthe electrolyte solution may comprise a non-flow cell electrolytesolution.

A nineteenth embodiment may include the secondary Zn—MnO₂ battery of theeighteenth embodiment, wherein the non-flow secondary Zn—MnO₂ batterymay comprise a prismatic configuration.

A twentieth embodiment may include the secondary Zn—MnO₂ battery of theeighteenth or nineteenth embodiments, wherein the non-flow cell Zn anodemay comprise a non-flow cell Zn anode mixture and a current collector,wherein the non-flow cell Zn anode mixture may be in electrical contactwith at least a portion of an outer surface of the current collector;and wherein the non-flow cell Zn anode may have a porosity of from about5 vol. % to about 90 vol. % based on the total volume of the non-flowcell Zn anode mixture of the non-flow cell Zn anode.

A twenty first embodiment may include the secondary Zn—MnO₂ battery ofthe twentieth embodiment, wherein the non-flow cell Zn anode mixture maycomprise Zn in an amount of from about 50 wt. % to about 90 wt. %, ZnOin an amount of from about 5 wt. % to about 20 wt. %, an electronicallyconductive material in an amount of from about 5 wt. % to about 20 wt.%, and a binder in an amount of from about 2 wt. % to about 10 wt. %,based on the total weight of the non-flow cell Zn anode mixture.

A twenty second embodiment may include the secondary Zn—MnO₂ battery ofany of the eighteenth to twenty first embodiments, wherein the non-flowcell Zn anode may comprise a pasted non-flow cell Zn anode.

A twenty third embodiment may include the secondary Zn—MnO₂ battery ofany of the eighteenth to twenty second embodiments, wherein the non-flowcell electrolyte solution may comprise a hydroxide, a potassiumhydroxide, a sodium hydroxide, a lithium hydroxide, or any combinationthereof in a concentration of from about 1 wt. % to about 50 wt. % basedon the total weight of the non-flow cell electrolyte solution.

A twenty fourth embodiment may include the secondary Zn—MnO₂ battery ofany of the eighteenth to twenty third embodiments, wherein the non-flowsecondary Zn—MnO₂ battery may be characterized by a cycle life of equalto or greater than about 5,000 cycles.

A twenty fifth embodiment may include the secondary Zn—MnO₂ battery ofany of the first to sixteenth embodiments, wherein the secondary Zn—MnO₂battery may comprise a flow-assisted secondary Zn—MnO₂ battery, whereinthe battery housing may comprise a flow-assisted battery housing,wherein the Zn anode may comprise a flow-assisted cell Zn anode, andwherein the electrolyte solution may comprise a flow-assisted cellelectrolyte solution.

A twenty sixth embodiment may include the secondary Zn—MnO₂ battery ofthe twenty fifth embodiment, wherein the flow-assisted secondary Zn—MnO₂battery may comprise a MnO₂ cathode plate, and wherein the plate hasflat surfaces.

A twenty seventh embodiment may include the secondary Zn—MnO₂ battery ofthe twenty fifth or twenty sixth embodiment, wherein the flow-assistedcell Zn anode may comprise electrodeposited Zn and a current collector,and wherein the electrodeposited Zn may be disposed on and is inelectrical contact with the current collector.

A twenty eighth embodiment may include the secondary Zn—MnO₂ battery ofany of the twenty fifth to twenty seventh embodiments, wherein theflow-assisted cell electrolyte solution may comprise a hydroxide,potassium hydroxide, sodium hydroxide, lithium hydroxide, orcombinations thereof in a concentration of from about 1 wt. % to about50 wt. % based on the total weight of the non-flow cell electrolytesolution, and wherein the flow-assisted cell electrolyte solution maycomprise ZnO in an amount of from about 0 g/L to about 200 g/L.

A twenty ninth embodiment may include the secondary Zn—MnO₂ battery ofany of the twenty fifth to twenty eighth embodiments, whereinflow-assisted secondary Zn—MnO₂ battery may be configured tocontinuously circulate the flow-assisted cell electrolyte solutionthrough the flow-assisted battery housing.

In a thirtieth embodiment, a method for producing energy comprisesdischarging a non-flow secondary Zn—MnO₂ battery to a discharge voltageto produce energy, charging the non-flow secondary Zn—MnO₂ battery to acharge voltage, and repeating the discharging and the charging of theflow-assisted secondary Zn—MnO₂ battery at least once. The non-flowsecondary Zn—MnO₂ battery comprises: a non-flow battery housing, a MnO₂cathode, a non-flow cell Zn anode, and a non-flow cell electrolytesolution. The MnO₂ cathode, the non-flow cell Zn anode, and the non-flowcell electrolyte solution are supported within the non-flow batteryhousing, and at least a portion of the Zn of the non-flow cell Zn anodeis oxidized during the discharging. At least a portion of the ZnO fromthe non-flow cell Zn anode mixture is reduced to Zn during the charging,and the non-flow secondary Zn—MnO₂ battery is characterized by a cyclelife of equal to or greater than about 5,000 cycles.

A thirty first embodiment may include the method of the thirtiethembodiment, wherein the MnO₂ cathode may comprise a MnO₂ cathode mixtureand a current collector, wherein the MnO₂ cathode mixture may be inelectrical contact with at least a portion of an outer surface of thecurrent collector, and wherein the MnO₂ cathode may have a porosity offrom about 5 vol. % to about 90 vol. % based on the total volume of theMnO₂ cathode mixture of the MnO₂ cathode.

A thirty second embodiment may include the method of the thirtieth orthirty first embodiment, wherein the non-flow cell Zn anode may comprisea non-flow cell Zn anode mixture and a current collector, wherein thenon-flow cell Zn anode mixture may be in electrical contact with atleast a portion of an outer surface of the current collector; andwherein the non-flow cell Zn anode may have a porosity of from about 5vol. % to about 90 vol. % based on the total volume of the non-flow cellZn anode mixture of the non-flow cell Zn anode.

A thirty third embodiment may include the method of any of the thirtiethto thirty second embodiments, wherein the non-flow cell Zn anode mixturemay comprise Zn in an amount of from about 50 wt. % to about 90 wt. %,ZnO in an amount of from about 5 wt. % to about 20 wt. %, anelectronically conductive material in an amount of from about 5 wt. % toabout 20 wt. %, and a binder in an amount of from about 2 wt. % to about10 wt. %, based on the total weight of the non-flow cell Zn anodemixture.

A thirty fourth embodiment may include the method of any of thethirtieth to thirty third embodiments, wherein the non-flow cellelectrolyte solution may comprise a hydroxide, a potassium hydroxide, asodium hydroxide, a lithium hydroxide, or any combination thereof in aconcentration of from about 1 wt. % to about 50 wt. % based on the totalweight of the non-flow cell electrolyte solution.

A thirty fifth embodiment may include the method of any of the thirtiethto thirty fourth embodiments, wherein the non-flow secondary Zn—MnO₂battery may be charged when assembled.

In a thirty sixth embodiment, a method for producing energy comprisescharging the flow-assisted secondary Zn—MnO2 battery to a chargevoltage, discharging the flow-assisted secondary Zn—MnO2 battery to adischarge voltage to produce energy, and continuously circulating theflow-assisted cell electrolyte solution through the flow-assistedbattery housing during the charging and the discharging. Theflow-assisted secondary Zn—MnO2 battery comprises: a flow-assistedbattery housing, a MnO2 cathode, a flow-assisted cell Zn anodecomprising a current collector, and a flow-assisted cell electrolytesolution. The MnO2 cathode, the flow-assisted cell Zn anode, and theflow-assisted cell electrolyte solution are supported within theflow-assisted battery housing, and ZnO from the flow-assisted cellelectrolyte solution is deposited as electrodeposited Zn on the currentcollector of the flow-assisted cell Zn anode during the charging. Atleast a portion of the electrodeposited Zn of the flow-assisted cell Znanode is oxidized and transferred back into the flow-assisted cellelectrolyte solution during the discharging.

A thirty seventh embodiment may include the method of the thirty sixthembodiment, further comprising: discharging the flow-assisted secondaryZn—MnO2 battery to a final voltage below the discharge voltage, whereinthe electrodeposited Zn of the flow-assisted cell Zn anode is completelyremoved from the current collector, and wherein continuously circulatingthe flow-assisted cell electrolyte solution through the flow-assistedbattery housing occurs during the discharging of the flow-assistedsecondary Zn—MnO2 battery to a final voltage below the dischargevoltage.

A thirty eighth embodiment may include the method of the thirty sixth orthirty seventh embodiment, wherein the MnO2 cathode may comprise a MnO2cathode mixture and a second current collector; wherein the MnO2 cathodemixture may be in electrical contact with at least a portion of an outersurface of the second current collector; wherein the MnO2 cathode mayhave a porosity of from about 5 vol. % to about 90 vol. % based on thetotal volume of the MnO2 cathode mixture of the MnO2 cathode.

A thirty ninth embodiment may include the method of any of the thirtysixth to thirty eighth embodiments, wherein the flow-assisted cellelectrolyte solution may comprise a hydroxide, a potassium hydroxide, asodium hydroxide, a lithium hydroxide, or any combination thereof in aconcentration of from about 1 wt. % to about 50 wt. % based on the totalweight of the non-flow cell electrolyte solution.

A fortieth embodiment may include the method of any of the thirty sixthto thirty ninth embodiments, wherein the flow-assisted cell electrolytesolution may comprise ZnO in an amount of from about 0 g/L to about 200g/L.

While embodiments of the invention have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Where numerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example,whenever a numerical range with a lower limit, R1, and an upper limit,Ru, is disclosed, any number falling within the range is specificallydisclosed. In particular, the following numbers within the range arespecifically disclosed: R=R1+k*(Ru-R1), wherein k is a variable rangingfrom 1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed. Use of the term “optionally” with respect to any element of aclaim is intended to mean that the subject element is required, oralternatively, is not required. Both alternatives are intended to bewithin the scope of the claim. Use of broader terms such as comprises,includes, having, etc. should be understood to provide support fornarrower terms such as consisting of, consisting essentially of,comprised substantially of, etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the embodiments of the present invention. Thediscussion of a reference in the Detailed Description of the Embodimentsis not an admission that it is prior art to the present invention,especially any reference that may have a publication date after thepriority date of this application. The disclosures of all patents,patent applications, and publications cited herein are herebyincorporated by reference, to the extent that they provide exemplary,procedural or other details supplementary to those set forth herein.

1. A secondary Zn—MnO₂ battery comprising: a battery housing; a MnO₂cathode; a Zn anode; and an electrolyte solution, wherein the MnO₂cathode, the Zn anode, and the electrolyte solution are disposed withinthe battery housing, wherein the MnO₂ cathode comprises a MnO₂ cathodemixture and a current collector, wherein the MnO₂ cathode mixture is inelectrical contact with at least a portion of an outer surface of thecurrent collector, and wherein the MnO₂ cathode has a porosity of fromabout 5 vol. % to about 90 vol. %, based on the total volume of the MnO₂cathode mixture of the MnO₂ cathode.
 2. The secondary Zn—MnO₂ battery ofclaim 1, wherein the Zn anode and the MnO₂ cathode capacities arebalanced.
 3. The secondary Zn—MnO₂ battery of claim 1, wherein at leastone of the Zn anode or the MnO₂ cathode comprises a pastedconfiguration.
 4. The secondary Zn—MnO₂ battery of claim 1, wherein atleast one of the MnO₂ cathode or the Zn anode have a thickness of fromabout 100 microns to about 1,000 microns.
 5. (canceled)
 6. The secondaryZn—MnO₂ battery of claim 1, wherein at least one of the MnO₂ cathode orthe Zn anode are further wrapped in an electrode separator membrane. 7.The secondary Zn—MnO₂ battery of claim 6, wherein the electrodeseparator membrane comprises a polymeric membrane, a sintered polymerfilm membrane, a polyolefin membrane, a polyolefin nonwoven membrane, acellulose membrane, a cellophane, a battery-grade cellophane, a sinteredpolyolefin film membrane, a hydrophilically modified polyolefinmembrane, or any combinations thereof.
 8. The secondary Zn—MnO₂ batteryof claim 1, wherein the MnO₂ cathode mixture comprises MnO₂ in an amountof from about 45 wt. % to about 80 wt. %, an electronically conductivematerial in an amount of from about 10 wt. % to about 45 wt. %, and abinder in an amount of from about 2 wt. % to about 10 wt. %, based on atotal weight of the MnO₂ cathode mixture.
 9. The secondary Zn—MnO₂battery of claim 8, wherein the MnO₂ comprises electrolytic manganesedioxide; wherein the electronically conductive material comprisescarbon, graphite, graphite powder, graphite powder flakes, graphitepowder spheroids, carbon black, activated carbon, conductive carbon,amorphous carbon, glassy carbon, or any combination thereof; and whereinthe binder comprises a polymer; a fluoropolymer, polytetrafluoroethylene(PTFE), a copolymer of tetrafluoroethylene and propylene; polyvinylidenefluoride (PVDF), a copolymer of styrene and butadiene, styrene-butadienerubber (SBR); a conducting polymer, polyaniline, polypyrrole,poly(3,4-ethylenedioxylthiophene) (PEDOT), copolymers of3,4-ethylenedioxylthiophene with various co-monomers (e.g., PEDOT withvarious dopants), a copolymer of 3,4-ethylenedioxylthiophene andstyrenesulfonate (PEDOT:PSS), polyvinyl alcohol (PVA), hydroxymethylcellulose (HMC), carboxymethyl cellulose (CMC), or any combinationthereof.
 10. The secondary Zn—MnO₂ battery of claim 1, wherein the MnO₂cathode mixture further comprises a metal, Bi, Sr, Ca, Ba, an oxidethereof, a hydroxides thereof, a nitrate thereof, a chlorides thereof,or any combination thereof.
 11. The secondary Zn—MnO₂ battery of claim1, wherein the MnO₂ cathode comprises a pasted MnO₂ cathode.
 12. Thesecondary Zn—MnO₂ battery of claim 1, wherein the MnO₂ cathode comprisesa first MnO₂ cathode dried sheet, a second MnO₂ cathode dried sheet, andthe current collector, wherein the first MnO₂ cathode dried sheet ispressed onto a first side of the current collector, wherein the secondMnO₂ cathode dried sheet is pressed onto a second side of the currentcollector, wherein the first and the second MnO₂ cathode dried sheetsare pressed onto their respective sides of the current collector at apressure of from about 3,000 psi to about 10,000 psi, and wherein theMnO₂ cathode mixture is in electrical contact with both the first sideand the second side of the current collector.
 13. The secondary Zn—MnO₂battery of claim 1, wherein the current collector comprises a porousmetal collector, a metal conductive mesh, a metal conductive interwovenmesh, a metal conductive expanded mesh, a metal conductive screen, ametal conductive plate, a metal conductive foil, a metal conductiveperforated plate, a metal conductive perforated foil, a metal conductiveperforated sheet, a sintered porous metal conductive sheet, a sinteredmetal conductive foam, an expanded conductive metal, a perforatedconductive metal, or any combination thereof.
 14. The secondary Zn—MnO₂battery of claim 1, wherein the current collector comprises a metalcollector pocketed assembly.
 15. The secondary Zn—MnO₂ battery of claim1, wherein the current collector comprises a current collector substratecomprising graphite, carbon, a metal, an alloy, steel, copper, nickel,silver, platinum, brass, or any combination thereof.
 16. The secondaryZn—MnO₂ battery of claim 15, wherein the current collector comprises ametal, nickel, silver, cadmium, tin, lead, bismuth, or any combinationsthereof deposited on the current collector substrate.
 17. The secondaryZn—MnO₂ battery of claim 1, wherein the current collector comprises acurrent collector tab, wherein the current collector tab is inelectrical contact with an outer surface of the MnO₂ cathode.
 18. Thesecondary Zn—MnO₂ battery of claim 1, wherein the secondary Zn—MnO₂battery comprises a non-flow secondary Zn—MnO₂ battery, wherein thebattery housing comprises a non-flow battery housing, wherein the Znanode comprises a non-flow cell Zn anode, and wherein the electrolytesolution comprises a non-flow cell electrolyte solution.
 19. (canceled)20. The secondary Zn—MnO₂ battery of claim 18, wherein the non-flow cellZn anode comprises a non-flow cell Zn anode mixture and a currentcollector, wherein the non-flow cell Zn anode mixture is in electricalcontact with at least a portion of an outer surface of the currentcollector; and wherein the non-flow cell Zn anode has a porosity of fromabout 5 vol. % to about 90 vol. % based on the total volume of thenon-flow cell Zn anode mixture of the non-flow cell Zn anode.
 21. Thesecondary Zn—MnO₂ battery of claim 20, wherein the non-flow cell Znanode mixture comprises Zn in an amount of from about 50 wt. % to about90 wt. %, ZnO in an amount of from about 5 wt. % to about 20 wt. %, anelectronically conductive material in an amount of from about 5 wt. % toabout 20 wt. %, and a binder in an amount of from about 2 wt. % to about10 wt. %, based on the total weight of the non-flow cell Zn anodemixture.
 22. The secondary Zn—MnO₂ battery of claim 18, wherein thenon-flow cell Zn anode comprises a pasted non-flow cell Zn anode. 23.The secondary Zn—MnO₂ battery of claim 18, wherein the non-flow cellelectrolyte solution comprises a hydroxide, a potassium hydroxide, asodium hydroxide, a lithium hydroxide, or any combination thereof in aconcentration of from about 1 wt. % to about 50 wt. % based on the totalweight of the non-flow cell electrolyte solution.
 24. The secondaryZn—MnO₂ battery of claim 18, wherein the non-flow secondary Zn—MnO₂battery is characterized by a cycle life of equal to or greater thanabout 5,000 cycles. 25.-29. (canceled)
 30. A method for producing energycomprising: discharging a non-flow secondary Zn—MnO₂ battery to adischarge voltage to produce energy, wherein the non-flow secondaryZn—MnO₂ battery comprises: a non-flow battery housing, a MnO₂ cathode, anon-flow cell Zn anode, and a non-flow cell electrolyte solution,wherein the MnO₂ cathode, the non-flow cell Zn anode, and the non-flowcell electrolyte solution are supported within the non-flow batteryhousing, and wherein at least a portion of the Zn of the non-flow cellZn anode is oxidized during the discharging; charging the non-flowsecondary Zn—MnO₂ battery to a charge voltage, wherein at least aportion of the ZnO from the non-flow cell Zn anode mixture is reduced toZn during the charging; and repeating the discharging and the chargingof the flow-assisted secondary Zn—MnO₂ battery at least once, whereinthe non-flow secondary Zn—MnO₂ battery is characterized by a cycle lifeof equal to or greater than about 5,000 cycles.
 31. The method of claim30, wherein the MnO₂ cathode comprises a MnO₂ cathode mixture and acurrent collector, wherein the MnO₂ cathode mixture is in electricalcontact with at least a portion of an outer surface of the currentcollector, and wherein the MnO₂ cathode has a porosity of from about 5vol. % to about 90 vol. % based on the total volume of the MnO₂ cathodemixture of the MnO₂ cathode.
 32. The method of claim 30, wherein thenon-flow cell Zn anode comprises a non-flow cell Zn anode mixture and acurrent collector, wherein the non-flow cell Zn anode mixture is inelectrical contact with at least a portion of an outer surface of thecurrent collector; and wherein the non-flow cell Zn anode has a porosityof from about 5 vol. % to about 90 vol. % based on the total volume ofthe non-flow cell Zn anode mixture of the non-flow cell Zn anode. 33.The method of claim 30, wherein the non-flow cell Zn anode mixturecomprises Zn in an amount of from about 50 wt. % to about 90 wt. %, ZnOin an amount of from about 5 wt. % to about 20 wt. %, an electronicallyconductive material in an amount of from about 5 wt. % to about 20 wt.%, and a binder in an amount of from about 2 wt. % to about 10 wt. %,based on the total weight of the non-flow cell Zn anode mixture.
 34. Themethod of claim 30, wherein the non-flow cell electrolyte solutioncomprises a hydroxide, a potassium hydroxide, a sodium hydroxide, alithium hydroxide, or any combination thereof in a concentration of fromabout 1 wt. % to about 50 wt. % based on the total weight of thenon-flow cell electrolyte solution.
 35. The method of claim 30, whereinthe non-flow secondary Zn—MnO₂ battery is charged when assembled.36.-40. (canceled)